Antiperspirant spray devices and compositions

ABSTRACT

A method of filling a hand held spray device is disclosed. The spray device includes a body having a reservoir. The method includes filling the reservoir with a first composition having a non-volatile silicone fluid, an antiperspirant active, an organoclay material, and at least one liquid activation enhancer having a Hansen Solubility Parameter for Hydrogen Bonding, δ h  between about 2 and about 6 and a light transmittance value greater than 90%. The method further includes filling the reservoir with a liquid fragrance material after the reservoir is filled with the first composition to form an antiperspirant composition, attaching a valve to the body; and filling the reservoir with a propellant, wherein the hand held spray device has a propellant concentration after filling from about 30% to about 90% by weight of the total fill of materials within the reservoir and the non-volatile silicone fluid has a concentration from about 30% to about 70% by weight of the antiperspirant composition.

TECHNICAL FIELD

One aspect of the invention relates generally to spray devicescontaining an antiperspirant composition and a propellant. Yet anotheraspect of the invention relates generally to methods of usingantiperspirant spray devices.

BACKGROUND OF THE INVENTION

Spray devices are generally well known in the art, some examples ofwhich are disclosed in U.S. Pat. Nos. 4,396,152 and 5,082,652. Aerosolspray devices that dispense an antiperspirant composition are also knownin the art. Various examples are described in U.S. Pat. Nos. 4,152,415;4,806,338; 4,840,786; 4,904,463; 4,935,224; 5,298,236; 5,605,682;5,814,309; 7,815,899; EP 674,899; and WO 96/04884; WO/2004/014330; WO2007/00184, commonly assigned U.S. Ser. No. 61/701,201 filed Sep. 14,2012 and U.S. Ser. No. 61/789,480 filed Mar. 15, 2013, the substances ofwhich are incorporated herein by reference.

Many aerosol antiperspirant users desire a product that provides one ormore of the following benefits: minimizes the appearance of residue onthe skin, has a dry rather than wet feel, has rapid perceived drying, isnot sticky, provides a cool/fresh feeling at time of application,provides long lasting wetness and/or odor protection, is provided in aform that is easily portable in purses or small bags (as some users mayapply the antiperspirant composition more than once a day) and minimizesthe gassy cloud that forms during dispensing. While the relativeimportance/desirability of these characteristics may vary bygeographical region and gender and not all users desire all or the sameset of characteristics, there appears to be a generally universal desireamong aerosol antiperspirant users for a dry rather than wet feel,minimizing the appearance of residue, and providing long lastingwetness/odor protection or efficacy.

While some currently marketed aerosol spray devices may provide at leastsome of these benefits to varying degrees, there are often a series oftradeoffs involved depending on the combination of ingredients used.

Significant settling and/or agglomeration of particulates in anantiperspirant composition may complicate delivery of a uniform dose ofthe antiperspirant active from an aerosol spray device.

It may thus be desirable, in some instances, for these antiperspirantcompositions to contain a clay material as a bulking or suspending agentin order to reduce settling/caking of particulates, particularly theantiperspirant active, and to aid redispersion of the particulates byshaking of the package prior to use.

The use of bulking and suspending agents, such as smectite clays andsilicas, in antiperspirant compositions is well known (see, e.g., AComparison of Smectite Clays in Underarm Products, Elementis SpecialitesBrochure© 2008 and U.S. Pat. Nos. 5,298,236; 4,935,224; 4,904,463;4,806,338; 4,152,416; and WO 96/04884). Smectite clays are typicallylayered minerals that comprise closely agglomerated individual platelets(see, e.g., Additives Reference Guide, Claytone® and Tixogel®Organoclays, Southern Clay Products brochure). In some instances, thesmectite clays used in antiperspirant compositions are organoclays,which are clays that have been modified by the addition of organicmoieties (e.g., alkyl quaterniary materials such as dimethyl distearylammonium chloride) to a portion of the platelet faces. The platelets aretypically separated in a shearing operation and then chemicallyactivated (e.g., by the addition of triethyl citrate, propylenecarbonate, etc.). The chemical activator facilitates the formation ofhydrogen bonds between the edges of adjacent platelets (see, e.g.,Rheological Additives in Cosmetics, Elementis Specialties brochure),thereby creating a network with a much larger volume than the originalraw material. This network may act as a bulking or suspending matrixthat may reduce the settling and/or caking of particulates in thecomposition and aid redispersion of the particulates upon shaking of thespray device. This may be particularly useful in an antiperspirantcomposition, as the aluminum salts are dense and tend to settle quicklyand/or may be prone to caking in the presence of moisture. Significantsettling and/or agglomeration of particulates in an antiperspirantcomposition may complicate delivery of a uniform dose of theantiperspirant active from an aerosol spray device. This may in turnnegatively impact skin feel or contribute to the appearance of a whiteresidue. Further, poor activation of the clay material may reduce flowof the antiperspirant composition into a dip tube and/or agglomeratesmay enter the dip tube and clog small orifices within the valve.

The use of liquid fragrance is also desirable in antiperspirantcompositions. While there are benefits to including a liquid fragrancematerial in an antiperspirant composition, it is believed that at leastsome liquid fragrance materials may negatively affect activation of aclay material. This may become more apparent as the liquid fragrancematerial concentration increases.

Many currently available aerosol antiperspirant compositions alsoincorporate a volatile liquid (e.g., cyclopentasiloxane) as a carrierfor the antiperspirant active. The volatile liquid evaporates followingapplication to the skin, resulting in a dry skin feel, but sometimesleaves behind a visible residue (the antiperspirant active) that issubject to flaking and/or transfer to clothing. Flaking (or transfer) ofthe antiperspirant active may also reduce antiperspirant efficacy. Itmay be possible to overcome this visible residue problem with the use ofnon-volatile silicones which may increase the substantivity of theantiperspirant composition and actives on the skin as well as decreasethe propensity for forming visible residue on skin. However, avoiding aperception of wetness post application, which is sometimes associatedwith the inclusion of non-volative silicones, must also be minimized.

Also in some instances it may be desirable to use different ranges ofpropellant concentrations. One the one hand some consumers like currentantiperspirant aerosol spray devices that are typically large (greaterthan 150 ml). These devices accommodate high propellant concentrationsand may contain a larger amount of antiperspirant composition. On theother hand some consumers like to use smaller spray devices that may becarried in small purses and the like. Like antiperspirant compositioncomponents, there are additional product tradeoffs involved with theselection of different propellant levels. For example, high propellantconcentrations (e.g., greater than 75% and often greater than 80%), maydilute the antiperspirant composition, which in turn may help reduce therisk of clogging by particulates in the antiperspirant composition(e.g., the antiperspirant active, silica, clays etc.). Higher propellantconcentration enhances the cool/fresh feeling at time of application dueto more liquid propellant depositing on the skin and subsequentlyvaporizing there from. However, a high propellant concentration alsoproduces a large volume of gas upon exiting the spray device resultingin a gassy cloud and/or a turbulent spray. Deposition efficiency (e.g.,the amount of antiperspirant active and/or fragrance deposited on skincompared to the amount dispensed) may in turn be reduced due to thelarge amount of antiperspirant active and/or fragrance lost to theenvironment via the gassy cloud rather than deposited on the skin. Ahigh propellant concentration may also result in solubilization ofliquid fragrance materials into the propellant during storage, resultingin more of the liquid fragrance material being lost to the environmentwith the propellant rather than deposited on the skin. Thesedisadvantages may be minimized depending on the selected propellantlevels.

It is believed that antiperspirant compositions comprising anon-volatile silicone fluid, a clay material, a liquid activationenhancer and optionally a clay activator and/or a liquid fragrancematerial, in combination with a range of propellant concentrations foruse in a spray device, may be useful for addressing one or more of theabove-described tradeoffs. These compositions may provide enhanceddispersion and uniform dosing of actives, minimize interactions betweenthe liquid fragrance and the clay, and decrease visible residue problemsvia use of non volatile silicones, etc.

Therefore, there is a continuing desire to provide an antiperspirantcomposition comprising a non-volatile silicone fluid, a clay material, aliquid activation enhancer, and optionally a liquid fragrance materialand/or a clay activator, for use in a spray device having a propellantconcentration. Still further, there is a continuing desire to provide anantiperspirant composition comprising a non-volatile silicone fluid, aclay material, a liquid activation enhancer, and optionally a liquidfragrance material and/or clay activator, for use in a spray devicehaving a propellant concentration less than about 70%. Still furtheryet, there is a continuing desire to provide improved making and fillingmethods for an antiperspirant composition comprising a non-volatilesilicone fluid, a clay material, and optionally a liquid activationenhancer, a liquid fragrance material, and/or a clay activator. Variousnon-limiting antiperspirant compositions and spray devices and methodsare described hereafter which may be suitable for addressing one or moreof these desires.

SUMMARY OF THE DISCLOSURE

In one aspect, a hand held spray device is disclosed, comprising: a bodycomprising a reservoir to house a total fill of material; an actuatorcomprising an actuator exit orifice; a valve in fluid communication withthe actuator exit orifice and the reservoir; a propellant stored in thereservoir, the propellant having a concentration from 30% to 70% byweight of the total fill of materials stored within the reservoir; anantiperspirant composition stored in the reservoir, the antiperspirantcomposition comprising a non-volatile silicone fluid having aconcentration from about 30% to about 70% by weight of theantiperspirant composition, an antiperspirant active, an organoclaymaterial and at least one liquid activation enhancer having a HansenSolubility Parameter for Hydrogen Bonding, δ_(h), between about 2 andabout 6 and a light transmittance value greater than 90%, and optionallya liquid fragrance material.

In another aspect a hand held spray device is disclosed, comprising: abody comprising a reservoir to house a total fill of materials; anactuator comprising an actuator exit orifice; a valve in fluidcommunication with the actuator exit orifice and the reservoir; apropellant stored in the reservoir, the propellant having aconcentration from 30% to 70% by weight of the total fill of materialsstored within the reservoir; and an antiperspirant composition stored inthe reservoir, the antiperspirant composition comprising a non-volatilesilicone fluid having a concentration from about 30% to 70% by weight ofthe antiperspirant composition, an antiperspirant active, an organoclaymaterial and at least one liquid activation enhancer having thefollowing formula (I):R₁—X—R₂

wherein R₁ contains from about 8 to about 20 carbon atoms, X is selectedfrom the group consisting of an alcohol, ester, amide and aryl group,and R₂ is selected from the group consisting of null, H, 1 to 4 carbonatoms, and C₆H₅.

In another aspect a hand held spray device is disclosed, comprising: abody comprising a reservoir to house a total fill of material; anactuator comprising an actuator exit orifice;

a valve in fluid communication with the actuator exit orifice and thereservoir; a propellant stored in the reservoir, the propellant having aconcentration from 72% to 90% by weight of the total fill of materialsstored within the reservoir; an antiperspirant composition stored in thereservoir, the antiperspirant composition comprising a non-volatilesilicone fluid having a concentration from about 30% to about 70% byweight of the antiperspirant composition, an antiperspirant active,greater than 1% substantially inert particulates, an organoclay materialand at least one liquid activation enhancer having a Hansen SolubilityParameter for Hydrogen Bonding, δ_(h), between about 2 and about 6 and alight transmittance value greater than 90%, and optionally a liquidfragrance material.

In another aspect a hand held spray device is disclosed, comprising: abody comprising a reservoir to house a total fill of materials; anactuator comprising an actuator exit orifice; a valve in fluidcommunication with the actuator exit orifice and the reservoir; apropellant stored in the reservoir, the propellant having aconcentration from 72% to 90% by weight of the total fill of materialsstored within the reservoir; and an antiperspirant composition stored inthe reservoir, the antiperspirant composition comprising a non-volatilesilicone fluid having a concentration from about 30% to about 70% byweight of the antiperspirant composition, an antiperspirant active,greater than 1% substantially inert particulates, an organoclay materialand at least one liquid activation enhancer having the following formula(I):R₁—X—R₂

wherein R₁ contains from about 8 to about 20 carbon atoms, X is selectedfrom the group consisting of an alcohol, ester, amide and aryl group,and R₂ is selected from the group consisting of null, hydrogen (H), 1 to4 carbon atoms, and C₆H₅.

In another embodiment a method for filling a hand held spray device isdisclosed, comprising: providing a body with a reservoir having a totalfill of materials;

mixing a non-volatile silicone fluid, an antiperspirant active, at leastone liquid activation enhancer and a first portion of an organoclaymaterial to form a first composition, wherein the liquid activationenhancer has a Hansen Solubility Parameter for Hydrogen Bonding, δ_(h),between about 2 and about 6 and a light transmittance value greater than90%; mixing a liquid fragrance material and a second portion of anorganoclay material to form a second composition; filling the reservoirby either mixing the first composition and the second composition toform an antiperspirant composition or by filling the reservoir with thefirst composition and thereafter filling the reservoir with the secondcomposition after the reservoir is filled with the first composition, toform an antiperspirant composition; providing a valve and attaching thevalve to the body; and filling the reservoir with a propellant having aconcentration of from about 30% to about 90% by weight of the total fillof materials.

In another embodiment a method of filling a hand held spray device isdisclosed, comprising: providing a body having a reservoir comprising atotal fill of materials; filling the reservoir with a first compositioncomprising a non-volatile silicone fluid, an antiperspirant active, anorganoclay material, and at least one liquid activation enhancer havinga Hansen Solubility Parameter for Hydrogen Bonding, δ_(h), between about2 and about 6 and a light transmittance value greater than 90%; fillingthe reservoir with a second composition comprising a liquid fragrancematerial after the reservoir is filled with the first composition toform an antiperspirant composition, wherein the non-volatile siliconefluid has a concentration from about 30% to about 70% by weight of theantiperspirant composition; providing a valve and attaching the valve tothe body; and filling the reservoir with a propellant, wherein the handheld spray device has a propellant concentration after filling fromabout 30% to about 90% by weight of the total fill of materials withinthe reservoir.

In another embodiment a hand held spray device is disclosed, comprising:a body comprising a reservoir comprising a total fill of materialsincluding a propellant and an antiperspirant composition; an actuatorcomprising an actuator exit orifice; a valve in fluid communication withthe actuator exit orifice and the reservoir; the propellant having aconcentration from about 30% to about 70% by weight of the total fill ofmaterials and a boiling point at 1 atmosphere from about −10° C. toabout 10° C.; and the antiperspirant composition comprising a liquidcarrier and an antiperspirant active.

BRIEF DESCRIPTION OF THE DRAWINGS

While the specification concludes with claims, it is believed that thesame will be better understood from the following description taken inconjunction with the accompanying drawings wherein like numbersillustrate like elements throughout the views and in which:

FIG. 1 is a bar graph illustrating various propellant concentrations v.percent fragrance deposition;

FIG. 2 is a 50× photomicrograph, taken using differential interferencecontrast, of a composition comprising 50 centistoke dimethicone,disteardimonium hectorite and triethyl citrate;

FIG. 3 is a 50× photomicrograph, taken using differential interferencecontrast, of a composition comprising cyclopentasiloxane,disteardimonium hectorite and triethyl citrate;

FIG. 4 is a 50× photomicrograph, taken using differential interferencecontrast, of a composition comprising 50 centistoke dimethicone,disteardimonium hectorite, triethyl citrate and a liquid fragrancematerial;

FIG. 5 is a 50× photomicrograph, taken using differential interferencecontrast, of a composition comprising cyclopentasiloxane disteardimoniumhectorite, triethyl citrate and a liquid fragrance material;

FIG. 6 is a 50× photomicrograph, taken using differential interferencecontrast, of a composition comprising 50 centistoke dimethicone,disteardimonium hectorite, triethyl citrate and isopropyl myristate;

FIG. 7 is a 50× photomicrograph, taken using differential interferencecontrast, of a composition comprising 50 centistoke dimethicone,disteardimonium hectorite, triethyl citrate, a liquid fragrance materialand isopropyl myristate;

FIG. 8 is a 50× photomicrograph, taken using differential interferencecontrast, of a composition comprising 50 centistoke dimethicone,disteardimonium hectorite, triethyl citrate, a liquid fragrance materialand octyldodecanol;

FIG. 9 is a 50× photomicrograph, taken using differential interferencecontrast, of a composition comprising 50 centistoke dimethicone,disteardimonium hectorite, triethyl citrate, a liquid fragrance materialand PPG-14 butyl ether;

FIG. 10 is a photograph showing three mixtures comprising 50 centistokedimethicone and C12-15 alkyl benzoate;

FIG. 11 is a photograph showing three mixtures comprising 5 centistokedimethicone and C12-15 alkyl benzoate;

FIG. 12 is a photograph showing five mixtures comprising 5 centistoke,10 centistoke, 20 centistoke, 50 centistoke or 350 centistokedimethicone and C12-15 alkyl benzoate;

FIG. 13 is a schematic illustration of a non-limiting example for makingan antiperspirant composition and the filling thereof into a reservoir;

FIG. 14 is a schematic illustration of another non-limiting example formaking an antiperspirant composition and the filling thereof into areservoir;

FIG. 15 is a schematic illustration of yet another non-limiting examplefor making an antiperspirant composition and the filling thereof into areservoir;

FIG. 16 is a cross-sectional side view of one non-limiting example of anovel spray device comprising an actuator, a valve assembly and areservoir containing a liquid propellant, a gaseous propellant and anantiperspirant composition;

FIG. 17 is a perspective view of the valve assembly of FIG. 16;

FIG. 18 is a side elevation view of the valve assembly of FIG. 17;

FIG. 19 is a cross-sectional view of the valve assembly of FIG. 18,taken along 5-5 thereof;

FIG. 20 is cross-sectional side elevation view of the valve stem of FIG.19;

FIG. 21 is a perspective view of the seal of FIG. 19;

FIG. 22 is a perspective view of the housing of FIG. 19;

FIG. 23 is a cross-sectional side elevation view of the housing of FIG.22, taken along line 9-9 thereof;

FIG. 24 is a perspective view of the insert of FIG. 19;

FIG. 25 is a cross-sectional side elevation view of the insert of FIG.24, taken along line 11-11 thereof; and

FIG. 26 is a bottom plan view of the insert of FIG. 24.

FIG. 27 is a bar graph illustrating formulations with various gumconcentrations v. percent deposition of antiperspirant composition ingrams.

DETAILED DESCRIPTION

A spray device, container, composition, propellant, etc. may comprise,consist essentially of, or consist of, various combinations of thematerials, features, structures, and/or characteristics describedherein.

Reference within the specification to “embodiment(s)” or the like meansthat a particular material, feature, structure and/or characteristicdescribed in connection with the embodiment is included in at least oneembodiment, optionally a number of embodiments, but it does not meanthat all embodiments incorporate the material, feature, structure,and/or characteristic described. Furthermore, materials, features,structures and/or characteristics may be combined in any suitable manneracross different embodiments, and materials, features, structures and/orcharacteristics may be omitted or substituted from what is described.Thus, embodiments and aspects described herein may comprise or becombinable with elements or components of other embodiments and/oraspects despite not being expressly exemplified in combination, unlessotherwise stated or an incompatibility is stated.

In all embodiments of the present invention, all percentages are byweight of the antiperspirant composition (or formulation), unlessspecifically stated otherwise. All ratios are weight ratios, unlessspecifically stated otherwise. All ranges are inclusive and combinable.The number of significant digits conveys neither a limitation on theindicated amounts nor on the accuracy of the measurements. All numericalamounts are understood to be modified by the word “about” unlessotherwise specifically indicated. Unless otherwise indicated, allmeasurements are understood to be made at approximately 25° C. and atambient conditions, where “ambient conditions” means conditions underabout 1 atmosphere of pressure and at about 50% relative humidity. Theterm “molecular weight” or “M.Wt.” as used herein refers to the numberaverage molecular weight unless otherwise stated.

The term “aerosol antiperspirant composition” refers to anantiperspirant composition that is pressurized and/or atomized by apropellant.

The term “aerosol spray device” refers to a spray device that uses apropellant to pressurize an antiperspirant composition and/or atomize anantiperspirant composition when sprayed.

The term “activated” refers to a clay material which has undergone avolume increase.

The term “antiperspirant composition” refers to any compositioncontaining an antiperspirant active and which is intended to be sprayedonto skin, exclusive of a propellant. An antiperspirant composition maybe provided in the form of a single phase, liquid dispersion (includingsuspensions, colloids, or solutions) as opposed to a two phase emulsion.

The term “antiperspirant efficacy” refers to the amount of wetnessprotection provided by application of an antiperspirant composition toan underarm area (or axillia) by a spray device. Antiperspirant efficacymay be quantified by the amount (mg) of sweat collected followingexposure to a hot room compared to a baseline amount.

The term “at the time of making” refers to a characteristic (e.g.,viscosity) of a raw material ingredient just prior to mixing with otheringredients.

The term “bulking or suspending material” refers to a material which isintended to reduce settling of a particulate from a liquid and/or reducethe severity of particulate caking post settling.

The terms “clay” and “clay material” refer generally to a variety of: i)clay minerals, including but not limited to the following groups: kaolin(e.g., kaolinite, dickite, halloysite, and nacrite), smectites (e.g.,montmorillonite, bentonite, nontronite, hectorite, saponite andsauconite), illites and chlorites; and ii) organoclay materials.

The term “clay activator” refers to a polar material which increases thevolume fraction of the clay material and/or the viscosity or yield pointof the antiperspirant composition.

The term “clogging” refers to: i) either a blocked passage, orifice,hole or other opening resulting in little or no mass flow out of acontainer when the actuator is activated, or ii) a valve stuck at leastpartially open from accumulated composition, resulting insemi-continuous or continuous leakage of the antiperspirant compositionand/or a propellant from the spray device, or iii) accumulation ofantiperspirant composition within a portion of the flow path of thecontainer which substantially impacts performance of the spray device.

The term “container” and derivatives thereof refers to the package thatis intended to store and dispense an antiperspirant composition in aspray type form. A container may typically comprise a reservoir forstoring the antiperspirant composition, a valve for controlling flow ofthe antiperspirant composition, and an actuator by which a user canactuate the valve.

The term “deposition efficiency” refers to the percentage of a material(e.g., antiperspirant active, fragrance material, antiperspirantcomposition, etc.) that is deposited on a target surface compared to theamount of material that exits in a spray device.

The term “particulate”, as used herein, refers to a material that issolid or hollow or porous (or a combination thereof) and which issubstantially or completely insoluble in the liquid materials of anantiperspirant composition.

The term “propellant” refers to one or more gases that are used topressurize the antiperspirant composition to facilitate egress of theantiperspirant composition from the container. Some propellants may be amixture of gases (e.g., A-46 which is a mixture of isobutane, butane andpropane). A propellant may be in the form of a liquid (i.e., a liquefiedgas) when under pressure within the reservoir of a spray device. Inaddition, a propellant may be in its gaseous state within the head spaceof the reservoir. A propellant may be present in both a liquefied formand its gaseous state within the reservoir. Unless specified otherwise(e.g., liquid propellant or gaseous propellant), the term propellant isintended to encompass the liquefied form and the gaseous stateindividually and collectively.

The term “substantially free of” refers to an amount of a material thatis less than 1%, 0.5%, 0.25%, 0.1%, 0.05%, 0.01%, or 0.001% by weight ofan antiperspirant composition. “Free of” refers to no detectable amountof the stated ingredient or thing.

The term “total fill” or “total fill of materials” refers to the totalamount of materials added to or stored within a reservoir(s) of acontainer. For example, total fill includes the propellant andantiperspirant composition stored within a spray device after completionof filling and prior to first use.

The term “viscosity” means dynamic viscosity (measured in centipoise,cPs, or Pascal-second, Pa·s) or kinematic viscosity (measured incentistokes, cSt, or m²/s) of a liquid at approximately 25° C. andambient conditions. Dynamic viscosity may be measured using a rotationalviscometer, such as a Brookfield Dial Reading Viscometer Model 1-2 RVTavailable from Brookfield Engineering Laboratories (USA) or othersubstitutable model known in the art. Typical Brookfield spindles whichmay be used include, without limitation, RV-7 at a spindle speed of 20rpm, recognizing that the exact spindle may be selected as needed by oneskilled in the art. Kinematic viscosity may be determined by dividingdynamic viscosity by the density of the liquid (at 25° C. and ambientconditions), as known in the art.

Without intending to be bound by any theory, it is believed thatsignificant antiperspirant efficacy and/or odor protection may beprovided by an antiperspirant composition comprising a non-volatilesilicone fluid (to provide good skin adherence) and optionally a liquidfragrance material optionally in combination with a propellantconcentration of from about 30% to about 90%, and in another embodimentless than about 70%, and in another embodiment less than 65% or 60%, byweight of the total fill of materials. In some embodiments, it may bedesirable for the antiperspirant composition to further comprise a claymaterial as a bulking/suspending agent to reduce particulate cakingand/or aid particulate redispersion and thereby reduce the risk ofclogging in the spray device and/or over-dosing and/or inconsistentdosing of the antiperspirant composition.

I. PROPELLANTS

A spray device comprises a propellant stored in one or more reservoirsof the container. The propellant may be stored in the same reservoir asan antiperspirant composition or a separate reservoir, although it ispreferred that the propellant is stored within the same reservoir as theantiperspirant composition. The propellant may be present in a liquefiedform that is miscible with liquid carriers of the antiperspirantcomposition as well as gaseous state within a head space of thereservoir. The liquid propellant and the antiperspirant composition forma mixture that travels thru container, eventually exiting the containerwhere the liquid propellant vaporizes to form a spray.

The propellant may have a concentration from about 30%, 32%, 34% 36%,38%, 40%, or 42% to about 90%, 85%, 80%, 75%, or 70%, by weight of thetotal fill of materials (i.e., propellant and antiperspirantcomposition) stored within the spray device.

In an embodiment, the propellant may have a concentration from about72%, 74%, or 76%, to about 80%, 85% or 90% by weight of the total fillof materials (i.e., propellant and antiperspirant composition).

In another embodiment the propellant may have a concentration from about30%, 32%, 34% 36%, 38%, 40%, or 42% to about 70%, 65%, 60%, 58%, 56%,54%, 52%, 50%, 48%, 46%, 44%, or 42% by weight of the total fill ofmaterials (i.e., propellant and antiperspirant composition) storedwithin the spray device.

In one embodiments the amount of liquid propellant (in grams) storedwithin a container may be from about 4 g, 6 g, 8 g, 10 g to about 45 g,25 g, 20 g, or 15 g. The volume of liquid propellant stored within thecontainer may be from about 10 mL, 20 mL, 30 mL, or 40 mL to about, 80mL, 70 mL, 60 mL, or 50 mL.

In another embodiment the propellant may have a concentration from 71%,72%, 74% 75%, 76%, 77%, or 79% to about 90%, 88%, 86%, 85%, 82%, or 80%by weight of the total fill of materials (i.e., propellant andantiperspirant composition) stored within the spray device. The amountof liquid propellant (in grams) stored within a container may be fromabout 50 g, 60 g, 70 g, 75 g, 80 g or 85 g to about 135 g, 125 g, 115 g,105 g, 95 g, or 90 g. The volume of liquid propellant stored within thecontainer may be from about 81 mL, 90 mL, 100 mL, 120 mL, 140 mL or 140mL to about 225 mL, 200 mL, 180 mL, 170 mL, 160 mL, or 150 mL.

Propellant concentration is one of many design variables that may affectperformance of an antiperspirant spray device. For example, propellantconcentration may impact the mass flow of the antiperspirantcomposition. The antiperspirant composition mass flow refers to thatportion of the total mass flow of the liquid propellant/antiperspirantcomposition mixture that is attributable to the antiperspirantcomposition. As propellant concentration decreases, the density of theliquid propellant/antiperspirant composition mixture increases. Saidanother way, the antiperspirant composition is less diluted by theliquid propellant. As a consequence, the ratio of antiperspirantcomposition to liquid propellant in the total mass flow of the mixtureincreases with decreasing propellant concentration. This effect is mostpronounced for hydrocarbon propellants (e.g., butane, isobutene,propane, etc.), which may have a density below that of theantiperspirant composition resulting in a larger volume fraction of thetotal mass flow. Decreasing propellant concentration may improveantiperspirant efficacy by: 1) increasing antiperspirant compositionmass flow (and hence the amount of antiperspirant active deposited onskin per use), and ii) reducing the amount of antiperspirant compositionlost to the environment in the form of a gassy cloud (due to less liquidpropellant vaporizing and/or a less turbulent spray).

Propellant concentration may also affect the amount of fragrancedeposited on skin. Many liquid fragrance materials are soluble in commonpropellants. As propellant concentration decreases, less of the liquidfragrance material may solubilize in the propellant during storage. Lesssolubilization may mean less of the fragrance material is lost to theenvironment as the liquid propellant turns to gas, and therefore moreliquid fragrance material may be deposited on the skin as part of theantiperspirant composition. This effect may be seen in FIG. 1, which isa graph of the amount of fragrance deposited on a blotter card forvarious propellant concentrations (e.g., 84%, 65%, and 50%) anddifferent propellants (e.g., A-46, A-31, and A-17, each propellanthaving a different equilibrium vapor pressure). The antiperspirantcomposition comprised dimethicone and a liquid fragrance materialcomprising known fragrance accords (at a total concentration of ˜5.5% byweight of the antiperspirant composition). The antiperspirantcomposition was sprayed onto commercially available aerosol perfumeblotter cards for a period of three seconds from a distance of ˜152 mm(6 inches). The total weight dispensed was determined by weighing boththe spray device and the blotter cards before and after dispensing. Theblotter cards were then individually placed in 125 ml I-chem jars, andthe perfume accords were extracted using hexane followed by analysis vialiquid injection gas chromatography with mass spectrometric detection todetermine the total amount of fragrance deposited, represented in FIG. 1along the y-axis as the percent deposited.

There appears to be a non-linear relationship in FIG. 1 between theamount of fragrance deposited at 84% propellant concentration and 65%propellant concentration compared to the amount of fragrance depositedat the 65% propellant concentration and the 50% propellantconcentration. This relationship appears generally consistent across thethree propellant types. It is believed that, in some instances, animprovement in fragrance deposition may be achieved at propellantconcentrations less than about 70%, 68%, 65%, 60%, 55%, or 50% by weightof the total fill of materials. This data might also suggest that it ispossible to reduce the concentration of the liquid fragrance material byabout 40% to 50% as propellant concentration drops from 84% to withinthe range of 70% to 65% while still maintaining about the same amount ofliquid fragrance deposition on skin.

Confoundingly, decreasing propellant concentration may involve a numberof negative tradeoffs. First, the lower antiperspirant compositiondilution that accompanies decreasing propellant concentration may resultin an antiperspirant composition/liquid propellant mixture that has ahigher concentration of particulates than a more diluted mixture. Thismay increase the risk of clogging within the small passages and orificesof a spray device, and further increases the desirability of providing abulking/suspending system that reduces caking of particulates and aidsredispersion thereof upon shaking. Second, increasing the antiperspirantcomposition mass flow rate too much may lead to over-dosing, which inturn can negatively impact skin feel (e.g., lead to a wet or sticky feelfrom the presence of too much antiperspirant active on skin) and/orincrease the likelihood of a visible residue. Third, it may be desirableto reduce the size of the one or more orifices and/or other flow areaswithin the container in order to prevent too high of an antiperspirantmass flow. Reducing the size of these flow areas may increase the riskof clogging however and is another reason for the desirability ofproviding a bulking/suspending system that reduces caking ofparticulates and aids redispersion thereof upon shaking. Fourth,decreasing the propellant concentration may diminish the cool/freshfeeling at time of application due to less liquid propellant depositingon the skin and subsequently vaporizing there from.

Propellant pressure is another design variable that may also affect themass flow of the antiperspirant composition/liquid propellant mixture.Different propellants will have different equilibrium pressures withinthe head space of a reservoir. For example, A-46 (which is a mixture ofisobutane, butane and propane) has an equilibrium pressure of 46 psig(317 kPa) while A-31 (which is isobutane) has an equilibrium pressure of31 psig (213 kPa). As propellant pressure within the head spacedecreases, the mass flow of the antiperspirant composition/liquidpropellant mixture correspondingly decreases (all other variables suchas flow path design being constant).

It is believed that propellant concentrations less than 30% by weight ofthe total fill of the container may result in too high of a mass flow ofthe antiperspirant composition and/or poor spray characterisitics (i.e.a narrow spray pattern). While reducing the controlling orificesize/area within the container may help offset some of theantiperspirant composition mass flow increase from reducing propellantconcentration, propellant concentrations less than 30% may requireorifice sizes that are so small that they may become susceptible toclogging and/or which may be more challenging to manufacture in a costeffective manner for commercial products.

A wide variety of propellants may be used with the spray devices andantiperspirant compositions described herein, although in someembodiments the spray device is substantially free of compressed gaspropellants such as nitrogen, air and carbon dioxide. Some suitableprimary propellants may have a boiling point (at atmospheric pressure)within the range of from about −45° C. to about 5° C. Some suitablepropellants may include chemically-inert hydrocarbons such as propane,n-butane, isobutane and cyclopropane, and mixtures thereof, as well ashalogenaed hydrocarbons such as dichlorodifluoromethane (propellant 12)1,1-dichloro-1,1,2,2-tetrafluoroethane (propellant 114),1-chloro-1,1-difluoro-2,2-trifluoroethane (propellant 115),1-chloro-1,1-difluoroethylene (propellant 142B), 1,1-difluoroethane(propellant 152A), dimethyl ether and monochlorodifluoromethane, andmixtures thereof. Some propellants suitable for use include, but are notlimited to, A-46 (a mixture of isobutane, butane and propane), A-31(isobutane), A-17 (n-butane), A-108 (propane), AP70 (a mixture ofpropane, isobutane and n-butane), AP40 (a mixture of propane, isobuteneand n-butane), AP30 (a mixture of propane, isobutane and n-butane),Br-46 (a mixture of butane, propane and isobutane), HFO1234(trans—1,3,3,3-tetrafluoropropene) and 152A (1,1difluoroethane).

While a wide variety of propellants may be used, there can be sometradeoffs associated with different propellants. For example, utilizinga propellant having boiling point less than −15° C. as a primarypropellant may, in some instances, be beneficial, because thesepropellants quickly expand to form a gas upon exiting the containerthereby creating a fine spray and higher spray forces (compared tohigher boiling point propellants) to deliver the antiperspirantcomposition to the target skin surface. Moreover, a propellant having alow boiling point and which is used at a high propellant concentrationmay result in adiabatic cooling of the antiperspirant composition uponexiting the spray device, aiding the creation of a desirable cool/freshsensation during application. However, it is believed that the use ofthese propellants at lower concentrations can result in less adiabaticcooling of the antiperspirant composition and a diminishment in thecool/fresh sensation. It is believed that propellants having boilingpoints higher than −15° C., used at lower propellant concentrations(e.g., less than about 70%), may provide improved cool/fresh sensationas more of the propellant deposits on the skin and evaporates therefrom,thereby aiding the creation of a cool/fresh sensation. However, too muchhigher boiling point propellant may deposit on the skin at higherpropellant concentrations, resulting in burning or irritation.

At propellant concentrations less than about 70% by weight of the totalfill of materials, it may be desirable in some instances for the primarypropellant to have a boiling point higher than −12° C., or from about−10° C., −5° C., 0° C. to about 10° C., 5° C. or 0° C. at 1 atmosphere.Propellants comprising n-butane, isobutane, pentane and isopentane maybe suitable for use at lower propellant concentrations. In someembodiments, the propellant may comprise more than 50% n-butane. In someembodiments, the propellant comprises a hydrocarbon blend having a vaporequilibrium pressure between about 45 kPa (about 6.5 psig) to about 175kPa (about 25 psig) at 25° C. Some non-limiting examples of preferredpropellants include A-17 and A-20. While these propellants may besuitable for use with the non-volatile silicone fluid antiperspirantcompositions described herein, it is believed that these propellants maybe suitable for use with other antiperspirant compositions (e.g.,comprising other liquid carriers, such as for example a volatilesilicone fluid in place of the non-volatile silicone fluid) atpropellant concentrations less than about 70%, or 65%, or 60% or 55% toprovide a clean/fresh sensation. Some non-limiting examples of otheraerosol antiperspirant compositions that may be used are described inU.S. Pat. Nos. 7,951,358; 2007/036,738; 2006/104,918; and 2003/211,060.

In some embodiments, it may also be desirable to provide a mixture ofpropellants having different boiling points. Combining a primarypropellant(s) having a boiling point less than 5° C. with a secondarypropellant(s) having a boiling point above 5° C. may increase thelikelihood of more liquid propellant reaching the skin surface. This inturn may enhance the cool/fresh sensation at time of application due tothe vaporization of the additional liquid propellant (e.g., thesecondary propellant) from the skin. The secondary propellant may have aconcentration from about 1% to about 20%, or from about 1% to about 15%,or from about 2% to about 10% by weight of the total fill of materialsin the product. The secondary propellant(s) may have a boiling pointfrom about 5° C., 10° C., 15° C., 20° C., or 25° C. to about 40° C., 35°C., or 30° C. In some embodiments, the secondary propellant(s) may havea boiling point greater than room temperature, or from 25° C. to 40° C.,which can further increase the likelihood that the secondarypropellant(s) reaches the skin and vaporizes thereat. Two non-limitingpropellants suitable for use as secondary propellants include pentaneand isopentane, although other propellants having boiling points withinthe ranges described herein may also be used.

In some embodiments, it may be desirable to utilize a propellant havingan equilibrium pressure, at about 25° C., from about 10 psig (69 kPa),15 psig (103 kPa), 20 psig (138 kPa), or 25 psig (172 kPa) to about 48psig (331 kPa), 46 psig (317 kPa), 40 psig (276 kPa), 34 psig (234 kPa)or 32 psig (220 kPA). A-46, A-31, A-20, A-17, and Br-46 are somepreferred propellants having equilibrium pressures within these ranges.In some instances, selecting a propellant with a lower equilibriumpressure may permit increasing the size of flow path restrictions tohelp reduce the risk of clogging without a concomitant increase in theantiperspirant composition mass flow that can accompany increasing thesize of a restriction. In some specific embodiments, A-31, A-20 or A-17may be preferred propellants for helping manage these interdependenttradeoffs.

II. ANTIPERSPIRANT COMPOSITIONS

A. Antiperspirant Composition Viscosity

In some embodiments, it may be desirable for the viscosity of theantiperspirant composition to be from about 1,000 centipoise, 2,000centipoise, or 3,000 centipoise to about 50,000 centipoise 40,000centipoise, or 30,000 centipoise, or 20,000 centipoise, or 10,000centipoise, or 5,000 centipoise or 4,000 centipoise at 25° C. (1centipose being equal to 1×10⁻³ Pa·s). It is believed that a viscositylower than 1,000 centipoise may lead to an antiperspirant composition,which when spayed, results in a runny or drippy effect on skin. This maybe perceived by a user as having a wet rather than dry feel. Forcomparison, roll-on type antiperspirant compositions often haveviscosities below 1,000 centipoise, because the roll-on applicatorutilizes a roller ball to apply a thin film of the antiperspirantcomposition thereby minimizing a runny or drippy effect. Since anantiperspirant composition should be flowable so that it may be sprayedeffectively from a spray device, the antiperspirant composition may bedevoid of ingredients in sufficient concentrations that provide anantiperspirant stick-type rheology. Some common agents which may beexcluded in meaningful amounts include hydrogenated castor oil, solidparaffins, silicone waxes, and mixtures thereof.

B. Non-Volatile Silicone Fluids

The antiperspirant compositions comprise one or more non-volatilesilicone fluids. The non-volatile silicone fluid may function as theprimary or principal liquid carrier for the antiperspirant active. Asused herein, the term “non-volatile” refers to a material that has aboiling point above 250° C. (at atmospheric pressure) and/or a vaporpressure below 0.1 mm Hg at 25° C. Conversely, the term “volatile”refers to a material that has a boiling point less than 250° C. (atatmospheric pressure) and/or a vapor pressure about 0.1 mm Hg at 25° C.Incorporating a non-volatile silicone fluid in an antiperspirantcomposition may provide several benefits. First, non volatile siliconefluids can be more effectively deposited on the skin than volatilesilicone fluids from aerosol antiperspirant compositions containing highlevels of propellant, such as greater than 70% or 80% propellant.Deposition of high concentrations of a non-volatile carrier fluid in theantiperspirant composition is believed to reduce visible white residueat application, reduce visible white residue throughout the day andreduce antiperspirant composition transfer to clothes while dressing.This can be illustrated by comparing the deposition of liquids from twotest samples. The first test sample comprises 85% A 46 propellant and15% cyclopentasiloxane by weight of the antiperspirant composition, andthe second comprises 85% A 46 and 15% of 50 centistoke dimethicone byweight of the antiperspirant composition. Both test samples used thesame valve and actuator combination. The first test sample comprisingcyclopentasiloxane had a deposition efficiency of about 24% and thesecond test sample comprising 50 centistoke dimethicone had a depositionefficiency of about 42%. This represents a 65% improvement in depositionby replacing the cyclopentasilicone with 50 cst dimethicone. While notbeing bound by any theory, it is believed that the lower deposition ofantiperspirant composition comprising cyclopentasiloxane may result fromboth inherent volatility of the volatile silicone fluid which can allowit to begin evaporating prior to deposition and a higher solubility ofthe antiperspirant composition in the propellant resulting in anincrease in the evaporation rate as the antiperspirant composition isco-vaporized with the propellant as both are expelled from thecontainer. Second, incorporating a non-volatile silicone fluid mayincrease the substantivity of the antiperspirant composition on skin,thereby potentially increasing antiperspirant efficacy, as theantiperspirant composition may form a film that more readily adheres toskin rather than flaking off or transferring to clothing throughout theday. Third, incorporating a non-volatile silicone fluid may alsodecrease the propensity for a visible residue to appear on skin(compared to using a volatile silicone fluid), as the non-volatilesilicone fluid does not evaporate thereby leaving behind the whiteantiperspirant active as a visible residue. However, incorporating anon-volatile silicone fluid is not without potential tradeoffs. Aperception of wetness post application (which may be undesirable forsome consumers) is one tradeoff that may be associated with highconcentrations of a non-volatile silicone fluid in an antiperspirantcomposition.

The total concentration of non-volatile, silicone fluids may be fromabout 30%, 35%, 40%, 45%, 50% to about 70%, 65%, 60%, 55% or 50% byweight of an antiperspirant composition. In some embodiments, the totalconcentration of non-volatile, silicone fluids may be from about 35% toabout 55% by weight of an antiperspirant composition. The liquidmaterials of the antiperspirant composition may consist essentially ofor primarily comprise a non-volatile, silicone fluid(s). Somenon-volatile, silicone fluids that may be used include, but are notlimited to, polyalkyl siloxanes, polyalkylaryl siloxanes, and polyethersiloxane copolymers, and mixtures thereof. Some preferred non-volatilesilicone fluids may be linear polyalkyl siloxanes, especiallypolydimethyl siloxanes (e.g., dimethicone). These siloxanes areavailable, for example, from Momentive Performance Materials, Inc.(Ohio, USA) under the tradename Element 14 PDMS (viscosity oil).Silicones Fluids from Dow Corning Corporation (Midland, Mich., USA)available under the trade name Dow Corning 200 Fluid series (e.g., 3 to350 centistokes). Other non-volatile silicone fluids that can be usedinclude polymethylphenylsiloxanes. These siloxanes are available, forexample, from the General Electric Company as SF 1075 methyl phenylfluid or from Dow Corning as 556 Fluid. A polyether siloxane copolymerthat may be used is, for example, a dimethyl polyoxyalkylene ethercopolymer fluid. Such copolymers are available, for example, from theGeneral Electric Company as SF-1066 organosilicone surfactant. Thenon-volatile, silicone fluid may have an average viscosity from about 3centistokes, 5 centistokes, 10 centistokes, 20 centistokes, or 50centistokes to about 350 centistokes, 200 centistokes, 100 centistokes,50 or 30 centistokes at 25° C. (1 centistoke being equal to 1×10⁻⁶m²/s). In some specific embodiments, the silicone fluid may have aviscosity from about 5 centistokes to about 100 centistokes or 5centistokes to about 50 centistokes or about 5 centistokes to about 30centistokes. In some instances, the non-volatile silicone fluid is apolydimethylsiloxane fluid (also commonly referred to as dimethicone).It will be appreciated that a polydimethylsiloxane fluid may be furthercharacterized by, optionally, its viscosity or its molecular weight orits formula or a combination thereof. In some instances, thepolydimethylsiloxane fluid may have the following characteristics:

TABLE 1 Approximate Approximate Average Number Molecular of MonomerUnits in the Viscosity Weight¹ Polymer¹  3 Centistokes 500 6  5Centistokes 800 9 10 Centistokes 1200 13 20 Centistokes 2000 27 30Centistokes 2600 35 50 Centistokes 3800 50 100 Centistokes  6000 80 200Centistokes  9400 125 350 Centistokes  13,700 185 ¹The compositions ofExamples 1 to 24 and FIGS. 1 to 12, to the extent they contained adimethicone fluid, were formulated utilitizing a Dow Corning DC200series fluid, which is believed to have had average molecule weights andaverage number of monomer subunits falling within the approcximatevalues of above-described table.The polydimethylsiloxane fluid may have the following formula (II):M—D_(X)—Mwherein M is (CH₃)₃SiO and D is 2CH₃(SiO) and X is equal to the averagenumber of monomer units (see, e.g., Table 1) in the polymer minus 2. Insome embodiments, X may be from about 6 to about 185, from about 9 toabout 125, from about 9 to about 80, from about 9 to about 50, fromabout 13 to about 50 or from about 27 to about 50. In other embodiments,X may be from about 6 to about 35, from about 9 to about 35 or fromabout 13 to about 35. The term “approximate” as used in Table 1 refersto ±10% of a given value.

While there are benefits to including a non-volatile silicone fluid, itis believed that a non-volatile silicone fluid may in some instancesnegatively affect activation of a clay material compared to a moretraditional liquid carrier, such as cyclopentasiloxane. An example ofthis effect may be seen by comparing FIGS. 2 and 3. FIG. 2 is aphotomicrograph illustrating the nature of the clay activation in acomposition comprising 50 centistokes dimethicone (about 86.5% w/w),disteardimonium hectorite (about 10.2% w/w) and triethyl citrate (about3.3% w/w), while FIG. 3 is a comparative photomicrograph illustratingthe nature of clay activation in a composition comprisingcyclopentasiloxane (about 86.5% w/w), disteardimonium hectorite (about10.2% w/w) and triethyl citrate (about 3.3% w/w). The composition ofFIG. 2 contains numerous agglomerations of the clay material (comparedto FIG. 3), illustrating the relatively poorer activation of the claymaterial compared to FIG. 3. Without intending to be bound by anytheory, it is believed that this poorer activation may result from weakinteractions between the dimethicone and the clay material. Dimethicone,like many non-volatile silicone fluids, has weak hydrogen bonding andVan der Waal forces, and as a result may be unable to easily interactwith or loosely bind to the modified or native portions of the claymaterial. This lack of interaction may result in clay plateletsinteracting too strongly with other clay platelets and formation of theagglomerates that are seen in FIG. 3.

This relatively poorer activation is further illustrated by comparativeExamples 1 and 4. The antiperspirant composition of Example 1 comprised,in part, cyclopentasiloxane (about 52.5% w/w), disteardimonium hectorite(about 4.25% w/w) and triethyl citrate (about 1.38% w/w). Theantiperspirant composition of Example 4 comprised, in part, 50centistoke dimethicone (about 52.5% w/w), disteardimonium hectorite(about 4.25% w/w) and triethyl citrate (about 1.38% w/w). Thedispersion/redispersion characteristics of an antiperspirant compositionmay be quantitatively/qualitatively assessed by measuring the height ofthe antiperspirant composition after long term settling (24 hours) andshort term settling (2 minutes) of the antiperspirant composition and/orby the number of rotations or turns of a glass bottle containing theantiperspirant composition that are needed to redisperse theantiperspirant composition. Better clay activation may be evidenced bygreater heights and/or lower turns. The antiperspirant composition ofExample 1 redispersed well with an average (n=3) of 6.3 turns, a longterm settling height of 17 mm and a short term settling height of 32 mm.In contrast, the antiperspirant composition of Example 4 dispersed morepoorly (in clumps) with an average (n=3) of 8 turns, a long termsettling height of 12 mm and short term settling height of 14 mm,substantially less than Example 1.

C. Liquid Fragrance Materials

An antiperspirant composition may also optionally comprise one or moreliquid fragrance materials. Liquid fragrance materials are typically amixture of perfume or aromatic components that are optionally mixed witha suitable solvent, diluent or carrier. Some or many of the perfumecomponents, when combined, may result in a highly polar liquid fragrancematerial. Some suitable solvents, diluents or carriers for the perfumecomponents may include ethanol, isopropanol, diethylene glycol monoethylether, dipropylene glycol, diethyl phthalate, triethyl citrate,isopropyl myristate and mixtures thereof. An antiperspirant compositionmay comprise from about 2%, 3% or 4% to about 10%, 8%, 6%, or 4% byweight of a liquid fragrance material.

Without intending to be bound by any theory, it is believed that, insome instances, a liquid fragrance concentration less than about 2% byweight of the antiperspirant composition may not deliver sufficient longlasting scent throughout the day For example, in some instances, it maybe desirable for the fragrance to last greater than 8 hrs, 10 hrs, 12hrs, 14 hrs or 16 hrs. Two antiperspirant formulas were tested in afragrance longevity test involving 68 panelists, who were employees ofthe assignee. This was a randomized, blinded, paired comparison testwhere half the panelists applied a control aerosol antiperspirantcomposition on the right underarm and half applied a control aerosolantiperspirant composition on the left underarm. Two blinded, testantiperspirant compositions were tested. The first antiperspirantcomposition comprised 50 centistoke dimethicone (49.5% w/w), aluminumchlorohydrate (about 26.4% w/w), a tapioca material (about 12% w/w),distreardimonium hectorite (about 4.2% w/w), isopropyl myristate (about4% w/w), a liquid fragrance material (about 2% w/w), triethyl citrate(about 1.4% w/w) and dimethicone/dimethiconol (about 0.5% w/w). Theliquid fragrance material also contained small amounts (about 15% orless by w/w of the liquid fragrance material) of isopropyl myristate asa diluent. The second antiperspirant composition comprised 50 centistokedimethicone (about 46.5% w/w), aluminum chlorohydrate (about 26.4% w/w),tapioca material (about 12% w/w), distreardimonium hectorite (about 4.2%w/w), isopropyl myristate (about 4% w/w), a liquid fragrance material(about 5% w/w), triethyl citrate (about 1.4% w/w) anddimethicone/dimethiconol (about 0.5% w/w). The liquid fragrance materialalso contained small amounts (about 15% or less by w/w of the liquidfragrance material) of isopropyl myristate as a diluent. Theantiperspirant composition was added to the reservoir of a spray devicealong with A-31 propellant to achieve a 35% w/w concentration of theantiperspirant composition and 65% w/w concentration of the propellant.The difference between the first and second antiperspirant compositionwas the concentration of liquid fragrance material and the concentrationof the dimethicone. Table 2 below sets forth the mean values (on a scalefrom 0 to 8, wherein 8 represents the strongest or most noticeableexperience) of the fragrance ratings by the panelists for the first andsecond antiperspirant compositions at the time of application, at 4 hrs,at the “change of shirt” (which may be from 8 to 16 hrs) and at thefollowing morning.

TABLE 2 First Second Antiperspirant Antiperspirant CompositionComposition (2% w/w Liquid (5% w/w Liquid Fragrance Fragrance Material)Material) Fragrance at application 5.7 7 Fragrance at 4 hrs 3.7 5.2Fragrance at change of shirt 2.4 3.5 Fragrance at 24 hrs 0.8 1.1Fresh/clean scent at application 6.4 7.5 Fresh/clean scent at 4 hrs 56.1 Fresh/clean scent at change of shirt 3.6 4.4 Fresh/clean scent at 24hrs 2.9 3.3

It is believed that a mean value greater 3.5 may be desirable forproviding an acceptable fragrance experience. It appears that, in atleast some instances, liquid fragrance material concentrations less thanabout 2% by weight of the antiperspirant composition may be lessdesirable for providing a long lasting scent experience at a “change ofshirt” time point and/or 24 hrs after application in antiperspirantcompositions comprising a non-volatile silicone fluid and propellantconcentration less than about 70% by weight of the total fill ofmaterials. Furthermore it is believed that fragrance levels less thanabout 4% may be less desirable for providing a long lasting scentexperience in antiperspirant compositions comprising a non-volatilesilicone fluid and propellant concentration more than 71% by weight ofthe total fill of materials.

The perfume component may be any natural or synthetic perfume componentknown to one skilled in the art of creating fragrances including, butnot limited to, essential oils, citrus oils, absolutes, resinoids,resins, concretes, etc., and synthetic perfume components such ashydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters,acetals, ketals, nitriles, etc., including saturated and unsaturatedcompounds, aliphatic, carbocyclic and heterocyclic compounds. Somenon-limiting examples of perfume components include: geraniol, geranylacetate, linalool, linalyl acetate, tetrahydrolinalool, citronellol,citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate,tetrahydromyrcenol, terpineol, terpinyl acetate, nopol, nopyl acetate,2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate,benzyl salicylate, benzyl benzoate, styrallyl acetate, amyl salicylate,dimethylbenzyl carbinol, trichloromethylphenyl-carbinyl acetate,p-tert.butyl-cyclohexyl acetate, isononyl acetate, vetiveryl acetate,vetiverol, alpha-n-amylcinammic aidehyde, alpha-hexylcinammic aldehyde,2-methyl-3-(p-tert.butylphenyl)-propanol,2-methyl-3-(p-isopropylphenyl)-propanal,3-(p-tert.butylphenyl)-propanal, tricyclodecenyl acetate,tricyclodecenyl propionate, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde, 4-(4-methyl-3-pentenyl)-3-cyclohexene carbaldehyde,4-acetoxy-3-pentyltetrahydropyran, methyldihydrojasmonate,2-n-heptylcyclopentanone, 3-methyl-2-pentylcyclopentanone, n-decanal,9-decenol-1, phenoxyethyl isobutyrate, phenyl-acetaldehyde dimethylacetal, phenylacetaldehyde diethyl acetal, geranonitrile,citronellonitrile, cedryl acetate, 3-isocamphylcyclohexanol, cedrylmethyl ether, isolongifolanone, aubepine nitrile, aubepine,heliotropine, coumarin, eugenol, vanillin, diphenyl oxide,hydroxycitronellal, ionones, methylionones, isomethylionones, irones,cis-3-hexenol and esters thereof, indane musk fragrances, tetralin muskfragrances, isochroman musk fragrances, macrocyclic ketones,macrolactone musk frangrances, ethylene brassylate, aromatic nitro-muskfragrances. Some perfume components are also described in Arctander,Perfume and Flavour Chemicals (Chemicals), Vol. I and II (1969) andArctander, Perfume and Flavour Materials of Natural Origin (1960).

While there are benefits to including a liquid fragrance material in anantiperspirant composition, it is believed that at least some fragrancematerials may negatively affect activation of a clay material andthereby further compound the negative effect introduced by anon-volatile silicone fluid. This may become more apparent as the liquidfragrance material concentration increases, particularly at higherliquid fragrance material concentrations (e.g., greater than about 2%w/w) that may be desirable in some instances. FIG. 4 is aphotomicrograph illustrating the nature of the clay activation in acomposition comprising 50 centistoke dimethicone (about 76.4% w/w),disteardimonium hectorite (about 9% w/w), triethyl citrate (about 2.9%w/w) and a liquid fragrance material (about 11.7% w/w). It is believedthat the liquid fragrance material also contained small amounts (about10% or less by w/w of the liquid fragrance material) of isopropylmyristate as a diluent. FIG. 5 is a comparative photomicrographillustrating the nature of clay activation in a composition comprisingcyclopentasiloxane (about 76.4% w/w), disteardimonium hectorite (about9% w/w/), triethyl citrate (about 2.9% w/w) and a liquid fragrancematerial (about 11.7% w/w). It is believed that the liquid fragrancematerial also contained small amounts (about 10% or less by w/w of theliquid fragrance material) of isopropyl myristate as a diluent. Thecomposition of FIG. 4 contains numerous agglomerations of the claymaterial compared to FIG. 5 (and even larger agglomerations thanobserved in FIG. 2), illustrating the relatively poorer activation ofthe clay material.

This relatively poorer activation associated with the addition of aliquid fragrance material is further illustrated by comparative Examples2 and 5. The composition of Example 2 comprised, in part,cyclopentasiloxane (about 47% w/w), disteardimonium hectorite (about4.25% w/w), triethyl citrate (about 1.38% w/w) and a liquid fragrancematerial (about 5.5% w/w). The antiperspirant composition of Example 5comprised, in part, 50 centistoke dimethicone (about 47% w/w),disteardimonium hectorite (about 4.25% w/w), triethyl citrate (about1.38% w/w) and a liquid fragrance material (about 5.5% w/w). Theantiperspirant composition of Example 2 redispersed well with an average(n=3) of 10 turns, a long term settling height of 15 mm and a short termsettling height of 42 mm. In contrast, the antiperspirant composition ofExample 5 dispersed more poorly (with clumps of the compositionremaining stuck on the bottom of the bottle even after 5 turns) with anaverage (n=3) of 19 turns, a long term settling height of 10 mm and ashort term settling height of 19 mm4. Without intending to be bound byany theory, it is believed that the combination of a non-volatilesilicone fluid, a liquid fragrance material and a clay material mayresult in less desirable clay activation compared to the combination ofa volatile silicone fluid, a liquid fragrance material and a claymaterial. It is further believed that polar liquid fragrance materialsmay more negatively impact clay activation, with the negative effectincreasing as the degree of polarity increases and as the concentrationof the liquid fragrance material increases. These disadvantages may beminimized, however, by including liquid activation enhancer, clayactivator, and/or by the method of addition steps, discussed herein.

D. Clay Materials and Clay Activators

An antiperspirant composition comprises a clay material as a bulking orsuspending agent. The concentration of clay material may be from about1%, 2%, 3% to about 8%, 6%, 5%, or 4% by weight of the antiperspirantcomposition. In some embodiments, the concentration of the clay materialis from about 2% to about 6% by weight of the antiperspirantcomposition. In some embodiments, the total particulates ofantiperspirant composition may comprise from about 5% to about 20% or 5%to 15% of a clay material. In some embodiments clay materials areorganoclays, which may be derived from clay minerals in which a portionof the inorganic cationic counter ions (e.g., sodium cations) of theclay mineral have been exchanged for organocations (e.g., quartenaryammonium chloride) thereby rendering the material organophilic ratherthan hydrophilic. Shearing/milling of the clay material deagglomeratesthe clay material platelets after which a polar clay activator may beadded in some instances to further separate the platelets and promotethe formation of hydrogen bonds between the edges of adjacent platelets.This enables formation of a higher volume three dimensional claystructure that suspends the particulates of the antiperspirantcomposition. This also increases the volume of the clay material in theantiperspirant composition, thereby increasing the volume or bulk of thetotal powder of the antiperspirant composition. This is also why thesettling height of an antiperspirant composition may be onequantitative/qualitative measure of the amount/quality of activation ofa clay material.

Some non-limiting examples of clay materials include montmorilloniteclays and hydrophobically treated montmorillonite clays. Montmorilloniteclays are those which contain the mineral montmorillonite and may becharacterized by a having a suspending lattice. Some examples of theseclays include but are not limited to bentonites, hectorites, andcolloidal magnesium aluminum silicates. Some non-limiting examples oforganoclays include modified bentonite, modified hectorite, modifiedmontorlinite and combinations thereof, some examples of which areavailable under the trade names Bentone 27 (stearalkonium bentonite),Bentone 34 (stearalkonium bentonite) and Bentone 38 (disteardimoniumhectorite) from Elementis Specialities Plc. and Tixogel VPV (quaternium90-bentonite), Tixogel VZV (stearalkonium bentonite), Tixogel LGM(stearalkonium bentonite) and Claytone SO (stearalkonium bentonite) fromSouthern Clay Products. In some instances, the bulking and suspendingmaterial consists substantially of, essentially of and/or primarily of aclay material and more preferably an organoclay material. In theseinstances, the antiperspirant composition may be substantially orcompletely free of silica materials used as a bulking/suspendingmaterial.

The antiperspirant composition may also comprise a clay activator, suchas propylene carbonate, triethyl citrate, methanol, ethanol, acetone,water and mixtures and derivatives thereof. Without intending to bebound by any theory, it is believed that the clay activator enhances thehydrogen bonds between the edges of adjacent clay platelets. Too littleclay activator may provide insufficient hydrogen bonding between clayplatelets while too much may create very strong interactions resultingin formation of agglomerates and loss of the desired bulking benefit.The clay activator may have a concentration ranging from 1:3 to 2:3parts clay activator to clay material. Clay activators may also stronglyinteract with an antiperspirant active (e.g., leading to clumping orcoating of the antiperspirant active and/or changes in active polymerstructure which may reduce antiperspirant efficacy). Therefore, it maybe desirable to limit the amount of clay activator present in theantiperspirant composition to between about 0.5%, 0.75%, 1%, 1.25%, or1.5% to about 3%, 2%, or 1.75% by weight of the antiperspirantcomposition.

E. Liquid Activation Enhancer

Without intending to be bound by any theory, it is believed that certainliquid materials may help maintain and/or promote the clay bulking andsuspending benefit in an antiperspirant composition that comprises anon-volatile silicone liquid, and optionally a liquid fragrancematerial, by facilitating increased interaction or loose bonding betweenthe non-volatile silicone fluid and the clay material. It is believedthat the increased interaction may be facilitated, in some instances,when the liquid activation enhancer is soluble in the non-volatilesilicone and has a Hansen Solubility Parameter for Hydrogen Bonding,δ_(h), between about 2 MPa^(1/2) and about 6 MPa^(1/2).

Liquid activation enhancers that are soluble in the non-volatilesilicone fluid may advantageously: 1) disperse within the non-volatilesilicone fluid, thereby promoting a more uniform interaction or loosebonding between the clay material and the non-volatile silicone fluid,and/or 2) minimize regions of high clay activation by increasing thesolubility and/or disperseability of the clay activator and/or optionalliquid fragrance material, thereby reducing the risk of locally highconcentrations of the clay activator and/or liquid fragrance materialwhich may result in clay precipitation. Solubility may be determined bymeasuring the amount of light transmittance (a light transmittancevalue) through a simple mixture of the non-volatile silicone fluid andliquid activation enhancer at the same weight/weight concentrations asin a final antiperspirant composition. For example, the solubility of aliquid activation enhancer at a concentration of 9% w/w in a finalantiperspirant composition comprising a non-volatile silicone fluidhaving a concentration of 38% w/w can be determined by measuring thelight transmittance of a simple mixture of the liquid activationenhancer at 19% w/w concentration in just the non-volatile siliconefluid. Light transmittance may be measured using a spectrophotometer,such as, for example, a Spectronic Genesys 10 V is Spectrophotometeravailable from Thermo Electron Corp (USA), wherein a light transmittancevalue greater than 80%, 85%, 90% or 95% at 25° C. indicates sufficientsolubility in the non-volatile silicone fluid.

It is also believed that a liquid activation enhancer having a δ_(h)value between 2 MPa^(1/2) and 6 MPa^(1/2) may also promote interactionor loose bonding between non-volatile silicone fluid and the claymaterial. It is believed that δ_(h) values less than about 2 MPa^(1/2)may be insufficient to provide adequate interaction or loose bondingbetween the non-volatile silicone fluid and the clay material whilevalues greater than about 6 may result in collapse of the threedimensional clay structure due to the creation of strong hydrogenbonding between the clay platelets. In some instances, it may also bedesirable that the liquid activation enhancer is also capable ofsolubilizing both the liquid fragrance material and the clay activatorin order to avoid regions of high/low clay activation, as thesematerials may not be easily solubilized in non-volatile silicone fluids.

An antiperspirant composition comprises at least one liquid activationenhancer. The at least one liquid activation enhancer, or thecombination of a plurality of activation enhancers, may have a totalconcentration from about 2%, 4%, 6%, 8%, 10% to about 30%, 25%, 20%,18%, 16%, 14%, 12%, 10% or 8% by weight of the antiperspirantcomposition. In some embodiments, the liquid activation enhancer has aconcentration from about 2% to about 15% by weight of the antiperspirantcomposition. It is believed that concentrations higher than 30% mayimpact spreading of the antiperspirant composition on skin by increasingthe surface tension of the composition, which is one mechanism by whicha dry skin feel may be imparted in an antiperspirant compositioncomprising a non-volatile silicone fluid. It also believed thatconcentrations less than 2% may be too low to provide sufficientinteraction between the clay material and the non-volatile siliconefluid

Some preferred liquid activation enhancers are molecules comprising afatty or hydrocarbon group and a functional group that is capable ofhydrogen bonding near or at one terminus of the hydrocarbon group. Thehydrocarbon chain may be from about 8 to about 20 carbon atoms in length(C₈ to C₂₀) to provide the desired solubility in the non-volatilesilicone fluid. The hydrocarbon chain may be linear, branched,unbranched, saturated or unsaturated. The hydrogen bonding group may beselected from the group consisting of alcohol, ester, amide andaryl/aromatic groups. Most preferred are hydrogen bonding acceptinggroups such as esters and aromatic groups. Some non-limiting examples ofthese materials include esters and amides formed from the reaction offatty acids, fatty amines, or fatty alcohols with alcohols, amines, orcarboxylic acids. Some non-limiting examples of fatty acids, fattyamines, and fatty alcohols include stearic acid, palmitic acid, myristicacid, lauric acid, stearyl amine, palmityl amine, myristyl amine,stearyl alcohol, palmityl alcohol, myristyl alcohol and lauryl alcohol.Some non-limiting examples of alcohols, amines, or carboxylic acidsinclude, methanol, ethanol, propanol, isopropanol, butanol, isobutanol,phenyl alcohol, benzyl alcohol, phenol, methyl amine, ethyl amine,propyl amine, butyl amine, benzyl amine, formic acid, acetic acid,propanoic acid, butyric acid and benzoic acid.

Some non-limiting examples of liquid activation enhancers includeisopropyl myristate, isopropyl palmitate, ethyl stearate, methylstearate, propyl stearate, butyl stearate, ethyl myristate, ethylpalmitate, butyl palmitate, propyl stearate, propyl palmitate, methylstearamide, ethyl stearamide, isopropyl stearamide, ethyl palmitamidepropyl palmitamide, stearyl benzoate, palmityl benzoate, C12-15 alkylbenzoate, benzyl palmitate, benzyl stearate, dodecylenbenezene andpalmityl acetate. Liquid activation enhancers might also include fattybranched chain alcohols and ethoxylated fatty alcohols. The liquidactivation enhancer may have the following formula (I):R₁—X—R₂

wherein R₁ contains from about 8 to about 20 carbon atoms, X is selectedfrom the group consisting of an alcohol, ester, amide and aryl groups,and R₂ is selected from the group consisting of null, hydrogen (H), 1 to4 carbon atoms, and C₆H₅.

Some particularly preferred non-limiting examples of liquid activationenhancers suitable for use include isopropyl myristate (δ_(h)=about2.95, light transmittance values about 101% at concentrations from 2% to30% w/w in 50 centistoke dimethicone), isopropyl palmitate (δ_(h)=about3.15, light transmittance values about 101% at concentrations from 2% to30% w/w in 50 centistoke dimethicone), butyl stearate (δ_(h)=about 3.45,light transmittance values about 100% at concentrations from 2% to 30%w/w in 50 centistoke dimethicone) and, in some instances, C12-15 alkylbenzoate (available under the trade name Finsolv® from InnospecPerformance Chemicals, USA) and combinations thereof. Turning first toisorpoyl myristate, FIG. 6 is a photomicrograph illustrating the natureof the clay activation in a composition comprising 50 centistokedimethicone (65% w/w), disteardimonium hectorite (10.2% w/w), triethylcitrate (2.9% w/w) and isopropyl myristate (21.5% w/w). FIGS. 6 and 3appear similar, thereby illustrating the beneficial effect of addingisopropyl myristate. FIG. 7 is a photomicrograph illustrating the natureof the clay activation in a composition comprising 50 centistokedimethicone (about 57.4% w/w), disteardimonium hectorite (about 9% w/w),triethyl citrate (about 2.9% w/w/), a isopropyl myristate (about 19%w/w) and a liquid fragrance material (about 11.7% w/w). It is believedthat the liquid fragrance material also contained small amounts (about10% or less by w/w of the liquid fragrance material) of isopropylmyristate as a diluent. The addition of the liquid fragrance materialdegraded somewhat the clay activation compared to FIG. 6, as evidencedby some agglomeration of the clay material, however the addition of theisopropyl myristate significantly improved the clay activation comparedto FIG. 4. The relatively better clay activation provided by theincorporation of isopropyl myristate is further illustrated by Examples7 and 8. The composition of Example 7 comprised, in part, 50 centistokedimethicone (about 43.5% w/w), isopropyl myrisate (about 9% w/w) anddisteardimonium hectorite (about 4.25% w/w). The composition of Example8 comprised, in part, 50 centistoke dimethicone (about 38% w/w),isopropyl myrisate (about 9% w/w), disteardimonium hectorite (about4.25% w/w) and a liquid fragrance material (about 5.5% w/w). Theantiperspirant composition of Example 7 redispersed well with an average(n=3) of 6.3 turns, a long term settling height of 17 mm and a shortterm settling height of 33 mm, which appear similar to the settling andredispersion characteristics of comparative Example 1. The addition ofthe liquid fragrance material in Example 8 resulted a long term settlingheight of 13 mm, an average (n=3) of 12 turns, and a short term settlingheight of 40 mm. These settling and redispersion characteristics appearto be an improvement over Example 5.

Turning now to Examples, 10 and 11, the relatively better clayactivation provided by the incorporation of isopropyl palmitate andbutyl stearate, respectively, are illustrated. The antiperspirantcomposition of Example 10 comprised, in part, 50 centistoke dimethicone(about 38% w/w), isopropyl palmitate (about 9% w/w), disteardimoniumhectorite (about 4.25% w/w) and a liquid fragrance material (about 5.5%w/w). The antiperspirant composition of Example 11 comprised, in part,50 centistoke dimethicone (about 38% w/w), butyl stearate (about 9%w/w), disteardimonium hectorite (about 4.25% w/w) and a liquid fragrancematerial (about 5.5% w/w). The antiperspirant composition of Example 10redispersed well with an average (n=3) of 8 turns, a long term settlingheight of 14 mm and a short term settling height of 38 mm, which issimilar to the settling and redispersion characteristics of Example 8.The antiperspirant composition of Example 11 also redispersed well withan average (n=3) of 9 turns, a long term settling height of 13 mm and ashort term settling height of 35 mm, which is also similar to thesettling and redispersion characteristics of Example 8. These settlingand redispersion characteristics appear to be improved compared toExample 5 and comparable to Example 8.

In contrast, comparative Examples 14 and 15 illustrate the relativelypoorer redispersion provided by the incorporation of mineral oil(δ_(h)=about 0.54, light transmittance values of about 100% atconcentrations from 2% and 15% w/w in 50 centistoke dimethicone andabout 0.4% at 30% w/w in 50 centistoke dimethicone) and isohexadecane(δ_(h)=about 0.21, light transmittance values of about 100% atconcentrations from 2% to 30% w/w in 50 centistoke dimethicone).Isohexadecane is soluble in 50 centistoke dimethicone across the 2% to30% w/w concentration range while mineral oil is soluble in 50centistoke dimethicone at some (lower) concentrations. Both materialshave δ_(h) values less than 2. The antiperspirant composition of Example14 comprised, in part, 50 centistoke dimethicone (about 38% w/w),mineral oil (about 9% w/w), disteardimonium hectorite (about 4.25% w/w)and a liquid fragrance material (about 5.5% w/w). The antiperspirantcomposition of Example 15 comprised, in part, 50 centistoke dimethicone(about 38% w/w), isohexadecane (about 9% w/w), disteardimonium hectorite(about 4.25% w/w) and a liquid fragrance material (about 5.5% w/w). Theantiperspirant compositions of Examples 14 and 15 fell off the bottom ofthe container in clumps and then redispersed with continued shaking, aless than desirable outcome compared to Example 8.

Comparative Examples 16 and 17 illustrate the relatively poorerredisperion provided by the incorporation of octyldodecanol (δ_(h)=about9.7, light transmittance values of about 100% at 2% w/w concentration in50 centistoke dimethicone and about 0.8% and about 0.6% at 15% and 30%,respectively, w/w concentration in 50 centistoke dimethicone) and PPG-14butyl ether (δ_(h)=about 6.52, light transmittance values of about 15%and about 0.9% at 2% to 30% w/w concentrations in 50 centistokedimethicone). Both of these materials have δ_(h) values greater than 6.Octydodecanol is soluble in the 50 centistoke dimethicone at some(lower) concentrations. PPG-14 butyl ether is insoluble in 50 centistokedimethicone across the 2% to 30% w/w concentration range. Theantiperspirant compositions of Examples 16 and 17 fell off the bottom ofthe container in clumps and then redispersed with continued shaking, aless than desirable outcome compared to Example 8. In addition, theantiperspirant composition of Examples 16 and 17 appeared grainy andnon-homogenous to the naked eye. FIG. 8 is a photomicrographillustrating the nature of the clay activation in a compositioncomprising 50 centistoke dimethicone (about 57.4% w/w), disteardimoniumhectorite (about 9% w/w), triethyl citrate (about 2.9% w/w),octyldodecanol (about 19% w/w) and a liquid fragrance material (about11.7%). It is believed that the liquid fragrance material also containedsmall amounts (about 10% or less by w/w of the liquid fragrancematerial) of isopropyl myristate as a diluent. In FIG. 8, the claycollapsed into clumps with no fine particles visible. This is arguablyworse than shown in FIG. 4, where at least some fine particles are stillvisible. FIG. 8 is also markedly worse than the composition shown inFIG. 7. FIG. 9 is a photomicrograph illustrating the nature of the clayactivation in a composition comprising 50 centistoke dimethicone (about57.4% w/w), disteardimonium hectorite (about 9% w/w), triethyl citrate(about 2.9% w/w), PPG-14 butyl ether (about 19% w/w) and a liquidfragrance material (about 11.7%). It is believed that the liquidfragrance material also contained small amounts (about 10% or less byw/w of the liquid fragrance material) of isopropyl myristate as adiluent. This composition resulted in macro agglomerates that werevisible to the naked eye and no fine particles, again markedly worsethan the composition shown in FIG. 7.

Some liquid materials may have a δ_(h) between 2 and 6 and straddle theline between soluble and not soluble in the non-volatile silicone fluid,depending on the w/w concentration of the material in the non-volatilesilicone fluid and/or the viscosity/molecular weight of the non-volatilesilicone fluid. One such material is C12-15 alkyl benzoate (δ_(h)=about4.7), available under the trade name Finsolv®. C12-15 alkyl benzoate haslight transmittance values of about 101%, about 102%, about 1.4% andabout 0.2% at concentrations of 2%, 9%, 15% and 30% w/w, respectively,in 50 centistoke dimethicone. Referring to FIG. 10, four mixtures of 50centistoke dimethicone and C12-15 alkyl benzoate at 2%, 9%, 15% and 30%w/w concentrations were prepared and are shown in the FIG. 10. The 2%w/w mixture is shown at the far left of FIG. 10 while the 30% w/wmixture is shown at the far right. The 9% and 15% w/w mixtures are shownsequentially to the right of the 2% w/w mixture in FIG. 10. The changein solubility between 9% w/w concentration and 15% w/w concentration isapparent from the change from relatively clear to a more milkyappearance of the mixture. Referring to Example 23, an antiperspirantcomposition comprising, in part, 50 centistoke dimethicone (about 38%w/w), C12-15 alkyl benzoate (about 9% w/w, which would be insoluble inthe non-volatile silicone fluid at this concentration), disteardimoniumhectorite (about 4.25% w/w) and a liquid fragrance material (about 5.5%w/w) was prepared. The antiperspirant composition exhibited poorerredispersion, with the antiperspirant composition falling off the bottomof the container in clumps.

In some instances, the liquid activation enhancer may also sufficientlyactivate the organoclay material without the need for a separate clayactivator, such as propylene carbonate, triethyl citrate, methanol,ethanol, acetone and mixtures and derivatives thereof. A non-limitingexample of one such material is C12-15 alkyl benzoate. Referring toExamples 21 and 22, two antiperspirant composition comprised, in part,20 centistoke dimethicone and C12-15 alkyl benzoate (9% w/w). Theantiperspirant composition of Example 21 comprised triethyl citrate andthe antiperspirant composition of Example 22 did not. Bothantiperspirant compositions had a powdery redispersion, indicating thatthe organoclay material was activated in both.

It is also believed that the viscosity of the non-volatile siliconefluid may in some instances impact the solubility of the liquidactivation enhancer in the non-volatile silicone fluid. In someembodiments, the viscosity of the non-volatile silicone fluid is fromabout 3 centistokes, 5 centistokes, 10 centistokes, 15 centistokes, 20centistokes, 50 centistokes and 100 centistokes to about 350centistokes, 200 centistokes, 100 centistokes or 50 centistokes.Preferably, the viscosity of the non-volatile silicone fluid is fromabout 5 centistokes to about 100 centistokes, more preferably betweenabout 5 centistokes and about 50 centistokes. In some embodiments, thenon-volatile silicone fluid has a viscosity from about 5 centistokes toabout 30 centistokes. In contrast to FIG. 10, FIG. 11 illustrates threemixtures of 5 centistoke dimethicone and C12-15 alkyl benzoate at 2%,15% and 30% w/w concentrations in the dimethicone. The 2% w/w mixture isshown at the far left of FIG. 11 while the 30% w/w mixture is shown atthe far right. The 15% w/w mixture is shown in the middle of FIG. 11.All the mixtures were relatively clear, and all of the mixtures havelight transmittance values of about 102%. Referring to FIG. 12, fourmixtures of 5 centistokes, 10 centistokes, 20 centistokes, 50centistokes and 350 centistokes dimethicone and C12-15 alkyl benzoate at15% w/w concentration were prepared. The 5 centistokes mixture is shownat the far left of FIG. 12 while the 350 centistokes mixture is shown atthe far right. The 10 centistokes, 20 centistokes and 50 centistokesmixtures are shown sequentially to the left of the 5 centistokes mixturein FIG. 12. The 5 centistokes mixture has a light transmittance value ofabout 102%, and the 10 centistokes mixture has a light transmittancevalue of about 100%. The 20 centistokes mixture has a lighttransmittance value of about 99%, and the 50 centistokes mixture has alight transmittance value of about 1.4%. The 350 centistokes mixture hada light transmittance value of about 0.4%. Referring to Examples 19, 20,21 and 23, these antiperspirant compositions comprised, in part, C12-15alkyl benzoate (about 9% w/w) in 5 centistoke dimethicone, 10 centistokedimethicone, 20 centistoke dimethicone and 50 centistoke dimethicone,respectively. The antiperspirant compositions of Examples 19, 20 and 21(in which the C12-15 alkyl benzoate was soluble in the non-volatilesilicone fluid) exhibited powdery redispersions while the antiperspirantcomposition of Example 23 (in which the C12-15 alkyl benzoate was notsoluble in the non-volatile silicone fluid) fell off the bottom of thecontainer in clumps.

Since both a non-volatile silicone fluid and a liquid fragrance materialmay negatively affect clay activation, it is believed that the at leastone liquid activation enhancer may be most beneficial in those instanceswhere the concentration of the liquid fragrance material exceeds theconcentration of the clay material and/or where the concentration of theliquid fragrance material exceeds the concentration of the clayactivator. In some embodiments, the ratio of total concentration ofnon-volatile silicone fluid to the total concentration of liquidactivation enhancer is from about 2:1 to about 10:1, or about 3:1 toabout 5:1.

F. Order of Addition of the Liquid Fragrance Materials and Non-VolatileSilicone Fluid

It is believed that the clay activation and desired bulking benefit maybe optionally further improved by controlling the order of addition ofthe liquid fragrance material and/or the clay material in the making ofan antiperspirant composition, particularly at liquid fragranceconcentrations greater than 2% by weight of the antiperspirantcomposition. Without intending to be bound by any theory, it is believedthat managing how the liquid fragrance material (particularly those thatare highly polar) is added/solubilized may reduce regions of high stronginteraction between the liquid fragrance material and the clay materialthat are believed to result in agglomeration of the clay material and/orprecipitation thereof. In one non-limiting embodiment and with referenceto FIG. 13, a making and filling process for an antiperspirantcomposition may comprise a plurality of steps. The first step comprisesoptionally mixing a first portion of the non-volatile silicone fluid(e.g., 10% to 30% of the total concentration of the final antiperspirantcomposition) with the clay material and the liquid activation enhancer.The second step comprises adding a clay activator to the mixture of thefirst step. It will be appreciated that, in some instances, a clayactivator may not be needed and this step may be skipped. This isfollowed by adding a second portion of the non-volatile silicone fluidin a third step, after which the particulates are added in a fourth stepto form a first composition. In this embodiment, the first compositionis then ready for the filling operation.

In the filling operation, the first composition from the makingoperation is filled into a reservoir of the spray device, after whichthe liquid fragrance material is added to the reservoir of the spraydevice to form the antiperspirant composition. When the liquid fragrancematerial and the first composition are added separately, as shown by wayof example in FIG. 13, there is believed to be little mixing between theliquid fragrance material and the antiperspirant composition due to thelarge viscosity difference between the two. The valve assembly is thenattached to the spray device after which the propellant is added to thereservoir through the valve assembly. Significant mixing of the liquidfragrance material and the first composition is not believed to occuruntil the addition of the propellant, which beneficially dilutes boththe liquid fragrance material and the first composition therebyminimizing regions of high liquid fragrance material concentration thatmay negatively impact the desired bulking benefit of the clay material.The last step may comprise attaching the actuator to the valve assembly.It will be appreciated that other ingredients may be added to thevarious mixtures at various points in either the making or fillingprocesses, including after the liquid fragrance material is added to thereservoir if desired.

Examples 3, 6 and 9 were made generally according to the process of FIG.13. The antiperspirant composition of Example 3 comprised, in part,cyclopentasiloxane (about 47% w/w/), distrearimonium hectorite (about4.25% w/w), triethyl citrate (about 1.38% w/w) and a liquid fragrancematerial (about 5.5% w/w). The antiperspirant composition had a powderyredispersion with average number of turns=7.3, a long term settlingheight of 14 mm and a short term settling height of 39 mm. Theantiperspirant composition of Example 6 comprised, in part, 50centistoke dimethicone (about 47% w/w), disteardimonium hectorite (about4.25% w/w), triethyl citrate (about 1.38% w/w) and a liquid fragrancematerial (about 5.5% w/w). The antiperspirant composition had poorredispersion with a majority of the composition still packed on thebottom of the bottle after 5 turns, a longer term settling height of 10mm and a short term settling height of 21 mm. The antiperspirantcomposition of Example 9 comprised, in part, 50 centistoke dimethicone(about 38% w/w), isopropyl myristate (about 9% w/w), distrearimoniumhectorite (about 4.25% w/w), triethyl citrate (1.38% w/w) and a liquidfragrance material (about 5.5% w/w). The composition had a powderyredispersion with an average number of turns=8, a long term settlingheight of 15 mm and a short term settling height of 40 mm. Notably,Example 9 appears to result in redispersion and settling characteristicscomparable to Example 3 and improved versus Example 6.

In another non-limiting embodiment and with reference to FIG. 14, amaking and filling process for an antiperspirant composition maycomprise a plurality of steps. The first step comprises optionallymixing a first portion of the non-volatile silicone fluid (e.g., 10% to30% of the total concentration of the final antiperspirant composition)with the clay material and the liquid activation enhancer. In someembodiments, the amount of clay material added in the first step is fromabout 50%, 60% or 70% to about 80% of the total amount of clay materialin the final antiperspirant composition post filling. In theseembodiments, from about 2.3% to about 3.75% of the clay material, byweight of the antiperspirant composition post filling, is added in thefirst step. The second step comprises adding a clay activator to themixture of the first step. It will be appreciated that, in someinstances, a clay activator may not be needed and this step may beskipped. This is followed by adding a second portion of the non-volatilesilicone fluid in a third step, after which the particulates togetherwith a liquid fragrance material and a second portion of the claymaterial (the liquid fragrance material and the second portion of theclay material having been pre-mixed) are added in a fourth step to formthe antiperspirant composition. Without intending to be bound by anytheory, it is believed that the perfume components of the liquidfragrance material that strongly interact with the second portion of theclay material may do so prior to mixing into the final antiperspirantcomposition and separate from the first portion of the clay materialthat was activated previously. It is believed that the bulking andsuspending benefit provided by the first portion of the clay materialmay not be significantly diminished. In this embodiment, the finalantiperspirant composition is then ready for the filling operation. Inthe filling operation, the final antiperspirant composition from themaking operation is filled into a reservoir of the spray device. Thelast step may comprise attaching the actuator to the valve assembly. Itwill be appreciated that other ingredients may be added to the variousmixtures at various points in either the making or filling processes ifdesired.

Example 24 was made generally according to the process of FIG. 14. Theantiperspirant composition of Example 24 comprised, in part, 50centistoke dimethicone (about 38% w/w/), distrearimonium hectorite(about 4.25% w/w), triethyl citrate (about 1.38% w/w) and a liquidfragrance material (about 5.5% w/w). The antiperspirant composition hada powdery redispersion with average number of turns=6, a long termsettling height of 12 mm and a short term settling height of 31 mm.

In yet another non-limiting embodiment and with reference to FIG. 15, amaking and filling process for an antiperspirant composition maycomprise a plurality of steps. The first step comprises mixing a firstportion of the clay material and optionally a first portion of thenon-volatile silicone fluid (e.g., 10% to 35% of the totalconcentration) together with a liquid activation enhancer. The clayactivator may be added as second step followed by a second portion ofthe non-volatile silicone fluid as a third step. It will be appreciatedthat, in some instances, a clay activator may not be needed and thisstep may be skipped. The particulates are added as a fourth step to forma first composition. In this embodiment, the first composition is thenready for the filling operation. In some embodiments, the amount of claymaterial added in the making process is from about 50%, 60% or 70% toabout 80% of the total amount of clay material in the finalantiperspirant composition post filling. In these embodiments, fromabout 2.3% to about 3.75% of the clay material, by weight of theantiperspirant composition post filling, is added during the makingprocess.

In the filling operation, the first composition from the makingoperation is filled into a reservoir of the spray device, after whichthe liquid fragrance material together with a second portion of the claymaterial (the liquid fragrance material and the second portion of theclay material having been premixed) are added to the reservoir of thespray device to form the antiperspirant composition. The second portionof the clay material and the liquid fragrance material are milled priorto adding to the reservoir as part of the filling operation. Withoutintending to be bound by any theory, it is believed that the perfumecomponents of the liquid fragrance material that strongly interact withthe second portion of the clay material may do so prior to filling thereservoir and separate from the first portion of the clay material thatwas activated as part of the making process. It is believed that thebulking and suspending benefit provided by the first portion of the claymaterial activated as part of the making process may not besignificantly diminished. The valve assembly is then attached to thespray device after which the propellant is added to the reservoir thruthe valve assembly. The last step may comprise attaching the actuator tothe valve assembly. It will be appreciated that other ingredients may beadded to the various mixtures at various points in either the making orfilling processes if desired.

The final antiperspirant compositions described in this Section F mayhave the same concentrations of ingredients, post filling (meaning afterall filling steps are complete), as otherwise described forantiperspirant compositions throughout this specification.

G. Particulate Materials

In one embodiment while the combination of low propellant concentrationand a high concentration of non-volatile silicone fluids may provide anumber of benefits, this combination may also involve a number oftradeoffs. For example, higher antiperspirant active deposition(facilitated by a low propellant concentration) in combination with ahigh concentration of a non-volatile silicone fluid may result in a wetand/or sticky skin feel. In addition, a non-volatile silicone fluid maytend to impede release of the antiperspirant active more so than avolatile liquid carrier, as a volatile liquid carrier eventuallyevaporates leaving behind the antiperspirant active and the othernon-volatile components, which are easily wetted by perspiration therebyreleasing the antiperspirant active. In contrast, non-volatile siliconesdo not evaporate as easily and tend to be hydrophobic, therebypotentially decreasing antiperspirant active release.

Delivering a sufficient concentration of particulates to the skin isbelieved to improve the skin feel of an antiperspirant compositioncomprising a high concentration of a non-volatile silicone fluid. It isbelieved that an antiperspirant composition comprising a totalnon-volatile liquid material to total particulate material ratio (L/Pratio) from about 0.6, 0.8, 1, 1.2, or 1.4 to about 2.3, 2.2, 2.1, 2,1.9, 1.8 or 1.6 may balance the tradeoff between enough particulates toprovide acceptable skin feel while minimizing the appearance of residue.An antiperspirant composition may have a total particulate concentrationfrom about 30%, 35%, or 40% to about 60%, 55%, or 50% by weight of theantiperspirant composition, in keeping with the total liquid to totalparticulate (L/P) ratios previously described. While increasing theconcentration of particulates may improve skin feel, it may also lead toan increased risk of clogging especially at low propellantconcentrations.

The antiperspirant composition may comprise a variety of particulatematerials. However, it is believed that the type (e.g., hydrophilic v.hydrophobic) and concentrations of particulate materials included in anantiperspirant composition may, in some instances, impact skin feel,release of the antiperspirant active, and the propensity for clogging inthe spray device. For example, too much antiperspirant active may resultin a wet or sticky skin feel due to the propensity of antiperspirantactives to become sticky when hydrated (e.g., by perspiration) evenwithin the L/P ratios previously described. In addition, too much of ahydrophobic particulate material may reduce release of theantiperspirant active from the composition. Conversely, inclusion of ahydrophilic particulate material may advantageously aid release of theantiperspirant active, which may be beneficial in a compositioncomprising a high concentration of a non-volatile silicone fluid.However, hydrophilic materials may increase the risk of clogging in thepresence of water. Therefore, it may be desirable to balance these andother design considerations when incorporating particulate materials inan antiperspirant composition comprising a non-volatile silicone fluidthat is in turn used in a spray device especially those with lowpropellant concentration.

Some examples of particulate materials include, but are not limited to,antiperspirant actives, powders (e.g., starch materials), encapsulatedfragrance materials and bulking or suspending agents (e.g., claymaterials). Other types of particulates may also be incorporated in anantiperspirant composition.

Antiperspirant Actives

An antiperspirant composition comprises one or more antiperspirantactives. The antiperspirant active may be any particle havingantiperspirant activity. The antiperspirant active is preferablyinsoluble in the liquid components of the antiperspirant composition.Since the amount of antiperspirant active may significantly impact skinfeel, an antiperspirant composition may comprise from about 14% 16%,18%, 20%, 22%, or 24% to about 38%, 36%, 34%, 32%, 30%, 28%, or 26% byweight of a particulate antiperspirant active. In some instances, it maybe desirable to utilize a low concentration of the antiperspirantactive, such as less than 20% or 18% by weight of the antiperspirantcomposition. The antiperspirant active concentrations refer to theanhydrous amount that is added. The antiperspirant active may representthe highest concentration of particulate materials in the antiperspirantcomposition. For example, the antiperspirant active (on an anhydrousbasis) may comprise from about 50% to about 80%, or from about 50% toabout 75%, or from about 55% to about 70% of the total particulatematerials in the antiperspirant composition. The balance of the totalparticulate concentration comprises non-antiperspirant activeparticulates.

Some examples of suitable antiperspirant actives include astringentmetallic salts, particularly including the inorganic and organic saltsof aluminum. Some non-limiting examples exemplary aluminum salts thatcan be used include aluminum chloride and the aluminum hydroxyhalideshaving the general formula Al₂(OH)_(a)Q_(b)XH₂0 where Q is chloride,bromide, or iodide (preferably chloride), a is from about 2 to about 5,and a+b=about 6, and a and b do not need to be integers, and where X isfrom about 1 to about 6, and X does not need to be an integer.Particularly preferred are the aluminum chlorhydroxides referred to as“5/6 basic chlorhydroxide” wherein “a” is 5 and “⅔ basic chlorhydroxide”wherein “a” is 4. Aluminum salts of this type can be prepared in themanner described more fully in U.S. Pat. Nos. 3,887,692; 3,904,741; and4,359,456. Preferred compounds include the ⅚ basic aluminum salts of theempirical formula Al₂(OH)₅DI2H₂0; mixtures of AlCl₃6H₂0 andAl₂(OH)₅CI₂H₂O with aluminum chloride to aluminum hydroxychloride weightratios of up to about 0.5.

The aluminum salt may be prepared by methods well known in the art. Insome embodiments, the aluminum salts may be made by applying heat to adilute aqueous solution of an aluminum salt (e.g., less than 20% of analuminum salt by weight of the dilute solution) to form a solid aluminumsalt comprising aluminum hydrolysis polymers. Some non-limiting examplesof such methods are described in U.S. Pat. Nos. 4,871,525 and 4,359,456.

Substantially Inert Particulate Materials

The balance of the total particulate concentration of an antiperspirantcomposition may comprise excipient particulate materials that aresubstantially inert with respect to the non-volatile silicone fluid. Theexcipient particulate materials may be either hydrophilic or hydrophobic(including hydrophobically modified, which tend to be moderatelyhydrophobic). Some non-limiting examples of substantially inertexcipient particulate materials that may be included in anantiperspirant composition include, but are not limited to, encapsulatedfragrance materials; native starches such as tapioca, corn, oat, potato,and wheat starch particulates; talc; calcium carbonate; perlite; micaand polyethylene beads.

The substantially inert particulates may be free flowing. Anantiperspirant composition may comprise from about 0.25%, 0.5%, 1%, 5%,10%, 12%, or 14% to about 25%, 22%, 20%, 18%, or 16% by weight of theantiperspirant composition of substantially inert particulates.

One substantially inert particulate material believed to be suitable foruse is a hydrophilic or hydrophobically modified tapioca material. Atapioca material may be particularly beneficial as it is unlikely toinduce an allergic reaction if inhaled. Tapioca is a starch which may beextracted from the cassava plant, typically from the root, which maythen be processed or modified as known in the art. Tapioca starches are,advantageously, substantially non-allergenic. One non-limiting exampleof a hydrophobically modified tapioca material suitable for usecomprises a silicone grafted tapioca starch, which is available underthe trade name Dry Flo TS from AkzoNobel of the Netherlands. The INCIname is tapioca starch polymethylsilsesquioxane and may be produced by areaction of methyl sodium siliconate (polymethylsilsesquioxane) andtapioca starch. This silicone grafted tapioca material is commerciallyavailable as CAS No. 68989-12-8. The silicone grafted tapioca materialcan be formed using any known means, including, but not limited to thosemethods described in U.S. Pat. Nos. 7,375,214, 7,799,909, 6,037,466,2,852,404, 5,672,699, and 5,776,476. Other non-limiting examples ofhydrophobically modified tapioca materials that are suitable for useinclude Dry Flo AF (silicone modified starch from Akzo Nobel), RheoplusPC 541 (Siam Modified Starch), Acistar RT starch (available fromCargill) and Lorenz 325, Lorenz 326, and Lorenz 810 (available fromLorenz of Brazil). In some specific embodiments, the tapioca materialmay be hydrophilic in order to facilitate release of the antiperspirantactive during use. One non-limiting example of a hydrophilic tapiocamaterial suitable for use is available under the trade name Tapioca Pureavailable from Akzo Nobel. In some specific embodiments, thesubstantially inert particulate material comprises a hydrophilic tapiocamaterial, a hydrophobic tapioca material or a mixture thereof.

An antiperspirant composition may optionally comprise one or moreparticulate fragrance carriers. Fragrance carriers are typicallyparticulates, which would be considered part of the total particulateconcentration of the antiperspirant composition. The fragrance carriersare preferably hydrophobic in order to minimize particle-to-particleinteractions. The fragrance carriers may be either full or empty. A fullfragrance carrier is a fragrance carrier that encapsulates or otherwisecontains a perfume component while the fragrance carrier is storedwithin the spray device. Full fragrance carriers may release theirperfume components by a variety of mechanisms post delivery from thespray device to provide a desired aroma or fragrance experience for auser. For example, the perfume components may be released by moistureupon wetting of the fragrance carrier, e.g., by perspiration or otherbody fluids. Alternatively or in addition thereto, the perfumecomponents may be released by fracture of the carrier, such as by theapplication of pressure or a shearing force. An empty fragrance carrieris a fragrance carrier that does not contain a perfume component whilestored within the spray device. One non-limiting example of an emptyfragrance carrier is an uncomplexed cyclodextrin material.

Some non-limiting examples of fragrance carriers suitable forencapsulating a perfume component include, but are not limited to,oligosaccharides (e.g., cyclodextrins), starches, polyethylenes,polayamides, polystyrenes, polyisoprenes, polycarbonates, polyesters,polyacrylates, vinyl polymers, silicas, and aluminosilicates. Someexamples of fragrance carriers are described in USPNs 2010/0104611;2010/0104613; 2010/0104612; 2011/0269658; 2011/0269657; 2011/0268802;U.S. Pat. Nos. 5,861,144; 5,711,941; 8,147,808; and 5,861,144.

An antiperspirant composition may comprise from about 0.25%, 0.5%,0.75%, 1%, or 2% to about 20%, 16%, 12%, 10%, 8%, 6% or 4% by weight ofthe antiperspirant composition of fragrance carriers. In some instances,the substantially inert excipient particles of the antiperspirantcomposition consist essentially of or completely of full fragrancecarriers, empty fragrance carrier, or mixtures thereof. Anantiperspirant may comprise from about 0.25%, 0.5%, 0.75%, or 1% toabout 6%, 4% or 2% by weight of the antiperspirant composition of fullfragrance carriers. An antiperspirant composition may comprise fromabout 0.25%, 0.5%, 1%, or 2% to about 16%, 12%, 10%, 8%, 6% or 4% byweight of the antiperspirant composition of empty fragrance carriers. Insome instances, it may be desirable to incorporate a mixture of emptyfragrance carriers and full fragrance carriers in the antiperspirantcomposition, wherein the empty fragrance carriers may be included toachieve the desired overall particulate concentration without the riskof perfume over-dosing.

In some instances, it may be desirable to provide a mixture of fragrancecarriers and native starch powders to achieve the desired particleconcentration. For example, from about a 20:80 to 80:20 (fragrancecarrier to starch) mixture might be utilized. In some instances, a 50:50mixture might be utilized and in other instances the native starchpowders might have a concentration equal to about or less than 6% byweight of the antiperspirant composition while the concentration of thefragrance carriers might be equal to about or less than 9% by weight ofthe antiperspirant composition.

A wide variety of perfume components may be used with the fragrancecarriers, including but not limited to volatile perfume componentshaving a boiling point at normal pressure of less than about 260° C.,more preferably less than about 250° C., and perfume components havingsignificant low odor detection threshold, and mixtures thereof. Theboiling points of many perfume components are given in, e.g., “Perfumeand Flavor Chemicals (Aroma Chemicals),” Steffen Arctander, published bythe author, 1969.

H. Other Liquid Materials

While it may be desirable for the liquid materials of the antiperspirantcomposition to consist essentially of or be primarily formed fromnon-volatile silicone fluids, the liquid activation enhancer andoptionally liquid fragrance materials, it is contemplated that otherliquid materials may be optionally included in an antiperspirantcomposition. The liquid materials of the antiperspirant composition maycomprise less than 30%, 20%, 10%, or less than 5% by weight of liquidmaterials other than non-volatile, silicone fluids. Said in another way,the liquid materials of the antiperspirant composition may comprise morethan 70%, 75%, 80%, 85%, 90% or about 100% by weight of non-volatilesilicone fluids.

It is believed that an antiperspirant composition whose liquid materialscomprise too much of a volatile silicone fluid may lead to an increasedpropensity for the appearance of a residue due to the evaporation of thevolatile silicone fluid. An antiperspirant composition may comprise lessthan 10%, 5%, 1%, or 0.5% by weight of a volatile silicone fluid. Anantiperspirant composition may be substantially or completely free of avolatile silicone fluid.

An antiperspirant composition may optionally comprise one or moresilicone gums. A silicone gum may be added to an antiperspirantcomposition to further increase substantivity of the antiperspirantcomposition and/or increase the drop size of the aerosol spray particlesand/or increase deposition on the skin. However, formulating anantiperspirant composition with a silicone gum in combination withrelatively high concentrations of a non-volatile silicone fluid and/orrelatively high concentrations of total particulates may involve anumber of tradeoffs. For example, too much of a silicone gum maydramatically increase viscosity of the antiperspirant composition andthe risk of clogging of the container actuator and/or valve,particularly where there is already a relatively high concentration oftotal particulates. Furthermore, too much of a silicone gum may reducethe diameter of the spray making it more difficult for a user to achievecomplete coverage of an axillia (typically a 7.5 cm×12.5 cm area) duringapplication as well as potentially creating regions of highantiperspirant composition dosage, thereby negatively impacting skinfeel. Still further, the amount of gum required to control thedeposition on skin and diameter of the spray pattern is dependent on thelevel and/or type of propellent, with the amount needed generallyincreasing as the propellant level and pressure increases.

Given the one or more potential challenges associated with incorporatinga silicone gum, an antiperspirant composition may be substantially orcompletely free of silicone gum materials. When inclusion of a siliconegum is desirable for antiperspirant products with less than about 70%propellant, an antiperspirant composition may have a concentration fromabout 0.05% or 0.075% to about 0.75%, 0.5%, 0.4%, 0.3%, or 0.2% of asilicone gum by weight of the antiperspirant composition. When inclusionof a silicone gum is desirable for antiperspirant products with morethan about 70% propellant, an antiperspirant composition may have aconcentration from about 0.3% or 0.5% to about 3.0%, 2.5%, 2%, 1.5%, or1.2% of a silicone gum by weight of the antiperspirant composition. Thesilicone gum material may have a viscosity from about 100,000centistokes to about 10,000,000 centistokes at 25° C.

If a silicone gum is included, any silicone gum having a viscositywithin the ranges described herein may be used, provided it is solublein the liquid carrier, propellant or a combination thereof of theantiperspirant composition. Some suitable silicone gums include siliconepolymers of the dimethyl polysiloxane type, which may have other groupsattached, such as phenyl, vinyl, cyano, or acrylic, but the methylgroups should be in a major proportion. Silicone polymers having aviscosity below about 100,000 centistokes (molecular weight below about100,000) at 25° C. are not considered silicone gums here but are rather,typically, considered a silicone fluid. One non-limiting example ofsilicone gum suitable for use is a silicone/gum fluid blend comprising adimethiconol gum having a molecular weight form about 200,000 to4,000,000 along with a silicone fluid carrier with a viscosity fromabout 0.65 to 100 mm² s⁻¹. An example of this silicone/gum blend isavailable from Dow Corning, Corp. of Michigan, USA under the trade nameDC-1503 Fluid or XIAMETER® PMX-1503 FLUID (85% dimethicone fluid/15%dimethiconol). Other silicone gums materials include SF1236 Dimethicone,SF1276 Dimethicone, and CF1251 Dimethicone available from MomentivePerformance Materials, Inc. of NY, USA.

An antiperspirant composition is preferably substantially or completelyfree of water added as separate ingredient (i.e., anhydrous), as toomuch added water may result in several deleterious effects such as: 1)increasing the propensity for antiperspirant active particulates toagglomerate (thereby increasing the propensity for clogging), and 2)reducing dry feel on skin. It will be appreciated that even an anhydrousantiperspirant composition may still contain some water that is boundwith an ingredient (e.g., antiperspirant active, tapioca material, etc.)otherwise added to the antiperspirant composition.

III. SPRAY DEVICES

As discussed above, there may be a variety of benefits and tradeoffsassociated with combining lower vs. higher propellant concentrationswith an antiperspirant composition comprising a non-volatile siliconefluid. For example reducing propellant concentration may increase theamount of antiperspirant active and/or fragrance materials that aredeposited on skin while enabling a more compact spray device. Regardlessof the level of propellant incorporating a non-volatile silicone fluidmay improve antiperspirant active substantivity on the skin. This maylead to an increase in antiperspirant efficacy or, alternatively, maypermit lower concentrations of antiperspirant active to be employed inan antiperspirant composition while still achieving comparableantiperspirant efficacy.

However, incorporating a non-volatile silicone fluid can lead to a wetfeeling in use, which may be disliked by some consumers. To compensate,sufficient particulate concentrations may improve skin feel to a point.However, a decrease in propellant concentration provides less dilutionof the antiperspirant composition and may necessitate reducing some flowareas within the spray device to limit the mass flows and avoidover-dosing of the antiperspirant composition. Reducing spray deviceflow areas may increase the risk of clogging.

In one embodiment in order to avoid over-dosing of the antiperspirantcomposition, for propellant concentrations from about 30% to about 70%,by weight of total fill of material, it is desirable that the spraydevice have a total mass flow rate of the propellant/antiperspirantcomposition mixture of less than 0.5 grams/sec or from about 0.1grams/sec to about 0.6 grams/sec, or from about 0.2 grams/sec to about0.4 grams/sec, or from about 0.25 grams/sec to about 0.35 grams/sec. Inanother embodiment for higher propellant concentrations, e.g from 70% toabout 90%, or from about 75% to about 90% by weight of total fill ofmaterial, in order to avoid over-dosing of the antiperspirantcomposition, it is desirable that the spray device have a total massflow rate of the propellant/antiperspirant composition mixture of lessthan 1.5 grams/sec or from about 0.5 grams/sec to about 1.25 grams/sec,or from about 0.7 grams/sec to about 1.1 grams/sec, or from about 0.8grams/sec to about 1.0 grams/sec. The spray device may have anantiperspirant composition mass flow rate less than 0.3 grams/sec orfrom about 0.1 grams/sec to about 0.3 grams/sec or from about 0.1grams/sec to 0.2 grams/sec or from about 0.15 grams/sec to about 0.2grams/sec. It is believed that mass flow rates greater than describedabove may lead to a wet or sticky skin feel (even if the L/P ratio iswithin the ranges previously described), because the total amount ofantiperspirant composition deposited on the skin may be too great.

The amount of antiperspirant active delivered to a target surface by atwo second application from a spray device may be from about 40 mg, 50mg, 60 mg, or 70 mg to about 110 mg, 100 mg, 90 mg, or 80 mg. The totalamount of antiperspirant composition delivered to a target surface by atwo second application of a spray device may be from about 0.1 grams toabout 0.4 grams, or from about 0.2 grams to about 0.4 grams, or fromabout 0.2 grams to about 0.3 grams. The amount of liquid fragrancematerial delivered to a target surface by a two second application of aspray device may be from about 3 mg to about 20 mg, or from about 6 mgto about 15 mg, or from about 6 mg to about 12 mg. The amount of fullfragrance carriers delivered to a target surface by a two secondapplication of a spray device may be from about 0.75 mg to about 15 mg,or from about 1 mg to about 12 mg, or from about 1 mg to about 9 mg. Thespray device may have a deposition efficiency, of either theantiperspirant composition and/or the antiperspirant active, that isfrom about 70% or 80% to about 95% or 90%.

Referring to FIG. 16, one non-limiting example of a spray device thatmay help reduce clogging in some instances is shown. While it may bedesirable to use the spray device shown in FIG. 16 to reduce the risk ofclogging in some instances, it will be appreciated that other spraydevices, including other types of actuators and valve assemblies, etc.,may also be used with the antiperspirant compositions and propellantsdescribed herein. The spray device 100 comprises a container 102, aliquid propellant 104 and an antiperspirant composition 106. It will beappreciated that the propellant 104 and antiperspirant composition 106are merely shown for purposes of illustration in FIG. 16, and FIG. 16 isnot intended to limit in any way the type or arrangement of thepropellant and antiperspirant composition within the container 102. Forexample, in some instances the propellant and the composition aremiscible such that distinct layers may not be visible. The spray device100 may be shaped and configured so that it is hand-holdable. Thecontainer 102 comprises a body 108, an actuator 110 having an actuatororifice 112, and a valve assembly 114 in fluid communication with areservoir 118 storing the composition 106 and liquid propellant 104. Thereservoir 118 may be defined by one or more interior surfaces of thebody 108. The reservoir may have a volume from about 20 ml, 40 ml, or 60ml to about 120 ml, 110 ml, 100 ml, or 90 ml. A dip tube 119 may extendinto the reservoir 118 from the valve assembly 114. A gaseous propellant120 may fill the headspace of the reservoir 118.

Referring to FIGS. 17 to 19, one non-limiting example of a valveassembly 114 which may be attached to the body 108 is shown. The valveassembly 114 comprises a slidably disposed valve stem 124 to which theactuator 110 attaches, a mounting flange 128 for attaching the valveassembly 114 to the body 108 (such as by crimping), and a housing 130attached to the mounting flange 128. The valve assembly 114 also has anaxial bore 144. The housing 130 may be attached by a variety of means tothe mounting flange, as known in the art, including by a press fit,positive latching, welding, etc. The housing 130 contains a spring 132that biases the valve stem 124. The spring 132 may comprise a pluralityof coils.

Turning to FIG. 20, the valve stem 124 comprises an upper portion 132and a lower portion 134. The upper portion 132 has a distal end 136 andis configured to be attachable to the actuator 110. The lower portion134 is configured to position at least a portion of the spring 132 thereabout. One or more valve stem orifices 138 (two being shown in theFIGS.) are disposed between the upper portion 132 and the lower portion134. The valve stem orifices 138 are arranged in a radial direction withrespect to the longitudinal axis 145 of the valve stem 124. The two ormore valve stem orifices 138 open into a wall 140 of a groove 142 andcommunicate with an axial bore 144 that extends from the two or morevalve stem orifices 138 to the distal end 136 of the upper portion 132.It will be appreciated that the terms “radial” and “axial”, andderivatives thereof (e.g., radially and axially), are intended to merelyrefer to a general direction with respect to a feature or structure, andthese terms are intended, unless expressly stated otherwise (e.g.,solely axial or solely radial), to be fully inclusive of directions thatare not purely radial or axial, such as substantially radial/axialdirections and combinations of radial and axial directions where the netoverall directional effect is more radial than axial or vice versa. Theaxial bore 144 in turn communicates with the actuator 110 when it isattached to the valve stem 124.

Referring to FIGS. 16, 19 and 21, mating sealing surfaces formed by aninner wall 146 of a substantially flat seal 148 and the wall 140 of thegroove 142 form a valve that seals the valve stem orifices 138. The seal148 may be formed from an elastomeric material, such as nitrilebutadiene rubber (sometimes referred to as Buna-N). The seal 148 may bedisposed about the valve stem and sandwiched between the mounting flange128 and the housing 130, as shown by way of example in FIG. 17. Thesealing surfaces are mated when the valve stem is not depressed, asshown in FIG. 17, thereby preventing flow of the antiperspirantcomposition/liquid propellant mixture thru the valve stem orifices 138.When the actuator 110 is depressed, the sealing surfaces separate,thereby permitting the antiperspirant composition/liquid propellantmixture to flow through the valve stem orifices 138 to the axial bore144 and onto the actuator 110. As used herein, the term valve (asopposed to valve assembly) is intended to merely refer to the matingsealing surfaces that prevent flow of the antiperspirantcomposition/liquid propellant mixture from the reservoir 118 to theactuator 110. The mating sealing surfaces may be provided inconfigurations other than shown in the FIGS and described herein. Insome specific embodiments, the valve may be a continuous flow valve,meaning there is flow through the valve for as long as the actuator isdepressed. In contrast, a non-continuous or metered valve allows onlypredetermined amount of flow thru the valve regardless how long theactuator is depressed.

Referring to FIGS. 18, 19 and 22 to 26, the housing 130 comprises a oneor more holes 150 for permitting gaseous propellant to pass from thehead space of the reservoir 118 into the interior of the housing 130.The housing 130 has a plurality of fingers 151 for attaching the housingto the mounting flange 128. An insert 152, which in some embodiments maybe cup-shaped, may be installed within the housing 130 between the diptube and the valve stem 124. The insert 152 may be press-fit within thehousing 130 or otherwise retained within the housing by other meansknown in the art. The insert 152 may receive one end of the spring 132.The insert 152 has an insert bore 154 disposed in a bottom wall 156 ofthe insert 152. The insert bore 154 is in fluid communication with thedip tube 119 and the interior of the insert 152 so that theantiperspirant composition/liquid propellant mixture may flow from thedip tube 119 to the interior of the insert 152. The mixture then flowspast the spring 132 and on to the valve.

A plurality of passages 158 are disposed between the dip tube 119 andthe distal end of the valve stem 124. While two passages are shown, itis contemplated that more than two passages may be provided. Thepassages 158 are disposed adjacent the dip tube exit and/or the tailorifice 160 (FIG. 19), the tail orifice 160 being disposed justdownstream of the dip tube exit. For purposes of clarity, the passages158 of valve assembly 114 are considered to be disposed adjacent the diptube 119 even though there is an intervening tail orifice 160 locatedbetween the dip tube exit and the passages 158. The passages 158 arepreferably located upstream of significant expansion of theantiperspirant composition/liquid propellant mixture. The passages 158may be disposed in a bottom surface 162 of the bottom wall 156 of thecup-shaped insert 158, and passage exits 164 are disposed adjacent tothe insert bore 154 and the tail orifice 160 so that gaseous propellantpassing through the passages 158 impinges the antiperspirantcomposition/liquid propellant mixture exiting the tail orifice 160. Inan embodiment, the passages 158 may be tangentially disposed the insertbore 154. The passages 158 are arranged in a manner to provide at leastsome, preferably significant, swirl or spin to the gaseous propellant asit exits the passages 158 and enters the insert bore 154 along with theantiperspirant composition/liquid propellant mixture. In some instances,the passages exits 164 direct the gaseous propellant in a directionsubstantially tangential to the flow of the antiperspirantcomposition/liquid propellant mixture exiting the dip tube 119 and/ortail orifice 160. The passages 158 may be arranged at an angle α fromabout 0 degrees (i.e., tangential, which is shown in FIG. 26) to about80 degrees, or 60 degrees, or 40 degrees, or 20 degrees, the angle αrepresenting the amount of angular deviation from a true tangentiallyarranged passage. The passages preferably have a length L sufficient todirect the gaseous propellant into swirling contact with theantiperspirant composition/liquid propellant mixture. While the passages158 are shown disposed in the bottom surface 162 of the insert 188, itis contemplated that the passages 158 may be provided by otherstructures/arrangements. Without intending to be bound by any theory, itis believed that the risk of clogging may be reduced in some instancesby one or more passages 158, disposed adjacent to the dip tube 119and/or tail orifice 160, that direct at least some of the gaseouspropellant from the reservoir into swirling contact (or which otherwiseimpart a spin to the gaseous propellant) with the antiperspirantcomposition/liquid propellant mixture. In some specific embodiments, thepassages may have a width of 0.01 inches and a height of 0.01 inches(0.25 mm) or a width of 0.01 inches (0.25 mm) and height of 0.013 inches(0.33 mm).

While clogging may occur at various locations within a spray device flowpath, the tail orifice 160, valve stem orifices 138, and actuatororifice 112 are believed to be some of the locations where clogging mayoccur. It is believed that balancing the flow area of the tail orifice160 and the propellant pressure to achieve the mass flow rates describedherein, rather than metering the flow rate at other locations in theflow path is, preferred as the size of the tail orifice 160 may still belarge enough reduce the risk of clogging while still being small enoughto effectively meter the mass flow rates to within the ranges describedherein. Conversely, it is believed that attempting to meter the massflow rates at the stem orifices 138 may lead to a higher risk ofclogging than metering at the tail orifice 160. In some specificembodiments, the tail orifice 160 has a diameter (or equivalentdiameter) from about 0.015 inches (0.38 mm) to 0.04 inches (1 mm) incombination with a propellant concentration from about 45% to about 65%and in further combination with a propellant pressure from about 15 psig(103 kPa) to about 46 psig (317 kPa). In some specific embodiments, thetail orifice 160 has a diameter (or equivalent diameter) from about0.015 inches (0.38 mm) to 0.03 inches (0.76 mm), or in other embodimentsfrom about 0.015 inches (0.38 mm) to 0.025 inches (0.64 mm), incombination with a propellant concentration from about 45% to about 55%and in further combination with a propellant pressure from about 15 psig(103 kPa) to about 32 psig (220 kPa), or in other embodiments from about15 psig (103 kPa) to about 20 psig (138 kPa).

Turning to the valve stem orifices 138, it is believed thatincorporating two opposing stem orifices having a diameter (orequivalent diameter) from about 0.012 inches (0.3 mm) to 0.016 inches(0.4 mm) in combination with the tail orifice diameters, propellantconcentrations, and propellant pressure combinations previouslydescribed may, in some instances, reduce the risk for clogging at thevalve stem while still achieving the desired mass flow rates.

The actuator exit orifice is another location that may be subject toclogging with the antiperspirant compositions, propellantconcentrations, propellant pressures, and mass flow rates describedherein. It is believed that an actuator orifice from about 0.014 inches(0.35 mm) to 0.02 inches (0.5 mm) or from about 0.014 inches (0.35 mm)to about 0.016 inches (0.4 mm) may reduce the risk for clogging at theactuator exit orifice while still achieving the desired mass flow rates.

One example of a valve assembly having the general configuration shownin FIG. 19 is available from the Precision Valve Company (USA) under thetrade name Ecosol.

IV. MEASUREMENT METHODS

Propellant Concentration

The overcap (if one is present) of the product container is removed, andthe weight of the container and its contents (gross mass) is measuredusing any suitable scale, such as an analytical balance. The top of thecontainer is punctured using any suitable tool, such as an AC-PD AerosolCan Puncturing Device available from Aero-Tech Laboratory EquipmentCompany, LLC of Missouri, USA. The puncture needle is fully extendedinto the container, and the puncture needle is slowly retracted topermit the gaseous propellant to evacuate the container. Once thepuncture needle is completely retracted from the container, thepuncturing device can be removed from the container, and the propellantwill continue to escape from the puncture in the container. All thepropellant is allowed to evacuate from the container.

The mass of the container and the remaining contents (less thepropellant) is measured using any suitable device, such as an analyticalbalance. The actuator is removed from the container using any suitabledevice, such as an Aero-Tech Can Decrimper available from Aero-TechLaboratory Equipment Company, LLC of Missouri, USA. The inside of thecontainer is rinsed with ethanol until visually clean and the containeris allowed to dry for at least 2 hours. The mass of the empty containerand actuator is measured using any suitable device, such as ananalytical balance. The propellant mass and concentration may bedetermined using the following equations:

Propellant  Mass  (g) = Gross  Mass − Mass  After  Propellant  Evacuation${{Propellant}\mspace{14mu}{Concentation}\mspace{14mu}\%} = \frac{{Propellant}\mspace{14mu}{Mass}}{{{Gross}\mspace{14mu}{Mass}} - {{Mass}\mspace{14mu}{of}\mspace{14mu}{Empty}\mspace{14mu}{Container}}}$

Total Mass Flow Rate

This measurement method is preferably utilized with aerosolantiperspirant products comprising a continuous actuator, meaningactuating the actuator results in a continuous rather than intermittentspray. At least four aerosol antiperspirant product samples are tested.The product samples are shaken as directed and the actuator is actuatedfor 2 to 3 seconds, after which each product sample is weighed tomeasure its mass using any suitable device, such as an analyticalbalance. The product samples are then immersed in a constant-temperature(25° C.) bath until the internal pressure stabilizes at a temperature of25° C. The product samples are then removed from the bath and excessmoisture is removed by blotting with a paper towel. The products samplesare shaken if directed and the actuator is actuated for 5 seconds, whichmay be accurately timed by use of a stopwatch. Each product sample isagain weighed, after which the product samples are returned to theconstant-temperature bath. The process of bathing, actuating, andweighing is repeated three times for each product sample. The averagetotal mass flow rate may be calculated from the spray time period (5.0seconds) and the difference in mass before and after each five secondspray, averaged across the four product samples and three repetitionsper product sample.

Antiperspirant Composition Mass Flow Rate

This measurement method is preferably utilized with aerosolantiperspirant products comprising a continuous actuator, meaningactuating the actuator results in a continuous rather than intermittentspray. At least four aerosol antiperspirant product samples are tested.The product samples are shaken if directed and then immersed in aconstant-temperature (25C) bath until the internal pressure stabilizesat a temperature of 25° C. The product samples are then removed from thebath and excess moisture is removed by blotting with a paper towel. Eachproduct sample is weighed to measure its mass using any suitable device,such as an analytical balance. Twelve large plastic bags (one for eachproduct sample times three repetitions) having a suitable volume, suchas a 1 L Ziploc brand bag (or a Whirl-Pak Write-on 55 ounce bag, Part #B01195WA available from Nasco, Inc), are weighed to measure their massusing any suitable device, such as an analytical balance. Each productsample is shaken if directed and sprayed into one of the bags for aperiod of 5 seconds in a manner that minimizes antiperspirantcomposition from exiting the bag. For example, the opening thru whichthe spray enters the bag may be limited to about 5 cm. The 5 secondspray time period may be accurately measured using a stopwatch.Following the 5 second spray period, the antiperspirant composition isallowed to settle within the bag and the bag remains open for at least 1minute but not longer than 2 minutes in order to allow the liquidpropellant to evaporate. The weight of the bags and their contents areweighed to measure their mass, and the product samples are also weighed.The average mass flow rate of the antiperspirant composition may bedetermined using the following equation which is averaged across thefour product samples and the three repetitions per product sample:

-   -   Mass Flow Rate of Antiperspirant Composition (g/sec)=Weight of        Bag and Antiperspirant Composition−Weight of Bag/5 seconds

Antiperspirant Composition Deposition Efficiency, Amount Dispensed, andAmount Deposited

At least four aerosol antiperspirant product samples are tested. Theproduct samples are shaken if directed and the actuator is actuated for2 to 3 seconds, after which each product sample is weighed to measureits mass using any suitable device, such as an analytical balance. Theproduct samples are then immersed in a constant-temperature (25° C.)bath until the internal pressure stabilizes at a temperature of 25° C.as determined by constancy of internal pressure. At least twelve filterpapers, such as Whatman 150 mm (diameter) Filter Paper available underthe catalog number 1003-150 from the Whatman Company of the UK, areweighed to measure the mass of the filter using any suitable device,such as an analytical balance. The product samples are removed from thebath, and any excess moisture is removed by blotting with a paper towel.The product samples are shaken if directed, and the product sample ispositioned approximately 15 cm away from one of the filter papers, whichis preferably weighted and/or fixtured to assure the filter paper doesnot move during spraying. The actuator of the product sample is actuatedfor 5 seconds which may be accurately timed using a stopwatch. It willbe appreciated, however, that other spray times may be substituted. Forexample, a two second spray time period might be used to betterapproximate the amount dispensed/deposited during a typical use cycle bya consumer. The spray from the product sample should be centered on thecenter of the filter paper. After spraying, the filter paper and productsample are weighed to measure the mass using any suitable device, suchas an analytical balance. The steps of bathing, weighing, and actuatingare repeated three times for each of the product samples. The averageantiperspirant composition efficiency may be calculated using thefollowing equations, averaged across the four product samples and thethree repetitions per product sample:

Amount  Dispensed  (g) = Product  Sample  Weight  Before  Spraying − Product  Sample  Weight  After  SprayingAmount  Deposited  (g) = Filter  Paper  Weight  After  Spraying − Filter  Paper  Weight  Before  Spraying${{Antiperspirant}\mspace{14mu}{Composition}\mspace{14mu}{Deposition}\mspace{14mu}{Efficiency}\mspace{14mu}(\%)} = {100 \times \frac{{Amount}\mspace{14mu}{Depositied}}{{Amount}\mspace{14mu}{Dispensed}*{Antiperpsirant}\mspace{14mu}{Composition}\mspace{14mu}{Weight}\mspace{14mu}\%}}$

Antiperspirant Active Deposition Efficiency, Amount Dispensed, andAmount Deposited

At least four aerosol antiperspirant product samples are tested. Theproduct samples are shaken if directed and the actuator is actuated for2 to 3 seconds, after which each product sample is weighed to measureits mass using any suitable device, such as an analytical balance. Theproduct samples are then immersed in a constant-temperature (25° C.)bath until the internal pressure stabilizes at a temperature of 25° C.The product samples are then removed from the bath and excess moistureis removed by blotting with a paper towel. At least twelve filterpapers, such as Whatman 150 mm Filter Paper available under the catalognumber 1003-150 from the Whatman Company of the UK, are weighed tomeasure the mass of the filter using any suitable devices, such as ananalytical balance. The product samples are removed from the bath, andany excess moisture is removed by blotting with a paper towel. Theproduct samples are shaken if directed, and the product sample ispositioned approximately 15 cm away from one of the filter papers, whichis preferably weighted and/or fixtured to assure the filter paper doesnot move during spraying. The actuator of the product sample is actuatedfor 5 seconds which may be accurately timed using a stopwatch. It willbe appreciated that other spray times may be substituted. For example, atwo second spray time period might be used to better approximate theamount dispensed/deposited during a typical use cycle by a consumer. Thespray from the product sample should be centered on the center of thefilter paper. After spraying, the filter paper and product sample areweighed to measure the mass using any suitable device, such as ananalytical balance. The steps of bathing, weighing, and actuating arerepeated three times for each of the product samples. The amount ofantiperspirant active deposited on a filter paper may be determinedusing an automated titrator, such as MettlerDL-70 equipped with MettlerDM141C combination silver-silver chloride electrode available fromMettler, Inc. Alternatively, the amount of antiperspirant activedeposited on a filter paper may be determined using the Content ofChloride Method set forth in the USP monograph for aluminumchlorohydrate (USP 35) or an equivalent method. The averageantiperspirant active deposition efficiency may be calculated using thefollowing equations, averaged across the four product samples and thethree repetitions per product sample:

Amount  Dispensed  (g) = Product  Sample  Weight  Before  Spraying − Product  Sample  Weight  After  SprayingAmount  Deposited  (gm) = Filter  Paper  Weight  Before  Spraying − Filter  Paper  Weight  After  Spraying${{Antiperspirant}\mspace{14mu}{Composition}\mspace{14mu}{Efficiency}\mspace{14mu}(\%)} = {100 \times \frac{{Amount}\mspace{14mu}{Depositied}}{{Amount}\mspace{14mu}{Dispensed}*{Antiperpsirant}\mspace{14mu}{Composition}\mspace{14mu}{Weight}\mspace{14mu}\%}}$

Long Term Settling Height and Short Term Settling Height

Long term settling height and short term settling height aredirectionally quantitative measures of the amount of bulking/suspendingprovided by a clay materials in an antiperspirant composition. Long termsettling height is the height of the antiperspirant composition aftersettling for 24 hours after shaking while short term settling height isthe height of the antiperspirant composition 2 minutes after shaking. 20grams of the antiperspirant composition into a clear glass aerosolcontainer (part number—ATL-SC4-48 from Aero-Tech Laboratory EquipmentCompany, LLC). The glass container had a diameter of 55 mm and a heightof 107 mm. The glass container is sealed with an appropriate valve. 40gms of isobutane propellant is added to the glass container through thevalve. The glass containers are shaken to completely disperse theantiperspirant composition and the glass containers are then hot tankedfor 4 minutes (130 F) to confirm the unit is completely sealed. Aftercooling, the glass containers are shaken again and allowed to stand for24 hrs.

To evaluate antiperspirant compositions that have been previously packedin other aerosol containers, the antiperspirant composition may beacquired by the following process. The overcap of the container isremoved. The top of the container is punctured using any suitable tool,such as an AC-PD Aerosol Can Puncturing Device available from Aero-TechLaboratory Equipment Company, LLC of Missouri, USA. The puncture needleis fully extended into the container, and the puncture needle is slowlyretracted to permit the gaseous propellant to evacuate the container.Once the puncture needle is completely retracted from the container, thepuncturing device can be removed from the container, and the propellantwill continue to escape from the puncture in the container. All thepropellant is allowed to evacuate from the container before removing 20grams of the remaining antiperspirant composition for addition to theglass container. It may be necessary to combine antiperspirantcomposition from multiple containers should there not be 20 grams ofmaterial in a single package.

The long term settling height is then easily measured using a clearruler (although any appropriated measuring device is possible) and isdefined as the distance from the top of the antiperspirant compositionpowder pack to its bottom. Care should be taken during this process toprevent significant agitation that would redisperse the powder pack. Theshort term settling height is measured by first shaking the glasscontainer vigorously for 30 seconds to achieve complete dispersion ofthe antiperspirant composition. The glass container is then placed on aflat surface without further agitation for 2 minutes (±5 seconds). Theshort term settling height is then easily measured at that time using aclear ruler (although any appropriated measuring device is possible) andis defined as the distance from the top of the antiperspirantcomposition powder pack to its bottom.

Redispersion

The redispersion characteristics of a composition may be measured by thenumber of turns of a transparent container that are need to redisperse acomposition that has undergone long term settling (24 hours per above).First, a composition is prepared and allowed to settle long term asprovided above. The number of turns is determined by slowly rotating thecontainer about its mid-point at a rate of approximately one fullrotation in two seconds. The number of full rotations or turns requiredto fully disperse the composition is recorded. Preferably, at leastthree sets of rotational tests are conducted to obtain an average valuefor the number of turns needed to fully redisperse the composition giventhere is some subjectivity as to when full redispersion occurs.Compositions having a well activated clay material should result inpowdery redispersion, meaning the particulates easily flowed away fromthe powder pack in a widely dispersed pattern during the first turn. Incontrast, compositions that are highly caked following long termsettling are more challenging to determine number of turns as clumps ofthe antiperspirant composition may fall off of the bottom and in theprocess aid break-up and redispersion. However, this phenomenonindicates a poorly activated clay material. For these reasons, thenumber of turns of a composition is one method for directionallyassessing the activation of a clay material.

Light Transmittance Value

Solubility of a liquid activation enhancer in a non-volatile siliconemay be determined by measuring the amount of light transmittance (lighttransmittance value) through a simple mixture of the non-volatilesilicone fluid and liquid activation enhancer at the same weight/weightconcentrations as in a final antiperspirant composition. For example,the solubility of a liquid activation enhancer at a concentration of 9%w/w in a final antiperspirant composition comprising a non-volatilesilicone fluid having a concentration of 38% w/w can be determined bymeasuring the light transmittance of a simple mixture of the liquidactivation enhancer at 19% w/w concentration in just the non-volatilesilicone fluid.

The light transmittance value using a spectrophotometer, such as, forexample, a Spectronic Genesys 10 V is Spectrophotometer available fromThermo Electron Corp (USA) or other similar spectrophotometer. TheSpectronic Genesys 10 V is utilizes a tungsten-halogen light source andhas a spectral bandwidth of 5 nm, a wavelength range of 325 to 1100 nm,accuracy of ±1 nm and a repeatability of ±0.5 nm. Readouts includeabsorbance, transmittance and concentration. The spectrophotometer isset to 640 nm wavelength and the percent transmittance mode/readout.Polystyrene spectrometer cuvettes having a 1 cm optical light path andtransmittance between ˜340 nm and ˜900 nm are used. One suitable exampleof a spectrometer cuvette is available from VWR International LLC underCatalog #97000-584 having a 2.5 to 4.5 ml capacity. Thespectrophotometer is calibrated according to the manufacturer'sinstructions using a reference cuvette and composition comprised of justthe non-volatile silicone fluid of interest. For example, if the testcomposition comprises 50 centistoke dimethicone and 15% w/w of isopropylmyristate, then the spectrometer is calibrated using a cuvettecontaining just 50 centistoke dimethicone. Sample cuvettes are filledsufficiently with a test composition of a non-volatile silicone fluidand liquid activation enhancer so that the light path of thespectrophotometer passes through the test composition in the cuvette.The sample cuvettes are shaken well just prior to taking a lighttransmittance reading. Light transmittance values greater than 80%, 85%,90% or 95% at 25° C. indicates solubility of the liquid activationenhancer in the non-volatile silicone fluid of the final antiperspirantcomposition.

V. EXAMPLES

The following examples are given solely for the purpose of illustrationand are not to be construed as limitations of the invention as manyvariations thereof are possible without departing from the spirit andthe scope of the invention.

Examples 1 to 9

Examples 1 to 6 describe some non-limiting comparative examples ofantiperspirant compositions, while Examples 7 to 9 describe somenon-limiting examples of antiperspirant compositions comprising a liquidactivation enhancer.

Ingredient EX 1 EX 2 EX 3 EX 4 EX 5 EX 6 EX 7 EX 8 EX 9 Aluminum 26.37% 26.37%  26.37%  26.37%  26.37%  26.37%  26.37%  26.37%  26.37% Chlorohydrate¹ Cyclopentasiloxane 52.5%   47%   47%   0%   0%   0%   0%  0%   0% Dimethicone²   0%   0%   0% 52.5%   47%   47% 43.5%   38%  38% Isopropyl Myristate   0%   0%   0%   0%   0%   0%   9%   9%   9%Hydrophilic tapioca   12%   12%   12%   12%   12%   12%   12%   12%  12% material³ Stearalkonium 4.25% 4.25% 4.25% 4.25% 4.25% 4.25% 4.25%4.25% 4.25% Hectorite⁴ Triethyl Citrate 1.38% 1.38% 1.38% 1.38% 1.38%1.38% 1.38% 1.38% 1.38% Silicone Gum⁵  0.5%  0.5%  0.5%  0.5%  0.5% 0.5%  0.5%  0.5%  0.5% Liquid Fragrance   0%  5.5%  5.5%   0%  5.5% 5.5%   0%  5.5%  5.5% Material⁶ Complexed Beta   3%   3%   3%   3%   3%  3%   3%   3%   3% Cyclodextrin Total 100 100 100 100 100 100 100 100100 ¹86% assay of anhydrous active, average particle size approximately15 microns. ²DC 200 Fluid (50 centistoke) available from Dow Corning³Tapioca Pure from Akzo Nobel ⁴Bentone 38 available from Elementis⁵DC1503 (a mixture of dimethicone and dimethiconol) available from DowCorning ⁶Is believed to have contained isopropyl myristate at less than10% w/w of the liquid fragrance material

Examples 1, 2, 4, 5, 7 and 8 were prepared by mixing a first portion ofthe cyclopentasiloxane or dimethicone, isopropyl myristate (if present)and disteardimonium hectorite by lightly stirring followed by millingfor at least 1 minute using a single head Silverson mill. The triethylcitrate was added next followed by at least five minutes of milling,followed by addition of the aluminum chlorohydrate, a second portion ofthe dimethicone, the complexed BCDs, tapioca material,dimethicone/dimethiconol and liquid fragrance material. After making thecomposition, approximately 20 gms thereof was added to a clear glassaerosol bottle (Part # ATL-SC4-48 available from Aero-Tech LaboratoryEquipment Co of USA). The glass bottle was sealed with a valve assemblyand then approximately 40 gms of isobutane propellant was added to thebottle thru the valve assembly. Each sample was shaken to disperse thecomposition and hot tanked for four minutes at 130° F. After cooling,the samples were shaken again and allowed to stand for 24 hrs (long termsettling) prior to rotational and short term settling testing. Examples3, 6 and 9 were prepared by mixing a first portion of thecyclopentasiloxane or dimethicone, isopropyl myristate (if present) anddisteardimonium hectorite by lightly stirring followed by milling for atleast 1 minute using a single head Silverson Mill. The triethyl citratewas added next followed by at least five minutes of milling, followed byaddition of the aluminum chlorohydrate, a second portion of thedimethicone, the complexed BCDs, tapioca material anddimethicone/dimethiconol. Approximately 18.9 gms of this mixture wasthen added to a clear glass aerosol bottle (Part # ATL-SC4-48 availablefrom Aero-Tech Laboratory Equipment Co of USA) followed by approximately1.1 gms of the liquid fragrance material. The glass bottle was sealedwith a valve assembly and then approximately 40 gms of isobutanepropellant was added to the bottle thru the valve assembly. Each samplewas shaken to disperse the composition and hot tanked for four minutesat 130F. After cooling, the samples were shaken again and allowed tostand for 24 hrs (long term settling) prior to rotational and short termsettling testing. Table 3 below sets forth the long term settlingheight, short term settling height, average turns and observationsrelated thereto for Examples 1 to 9.

TABLE 3 Long Term Short Term Settling Settling Average Height HeightTurns (mm) (mm) (N = 3) Observations EX 1 17 32 6.3 Powdery redispersionEX 2 15 40 10 Powdery redispersion EX 3 14 39 7.3 Powdery redispersionEX 4 12 14 8 Composition falls off of the bottom in clumps and thenredisperses EX 5 10 19 26 Majority of composition still packed on bottomafter 5 turns EX 6 10 21 22 Majority of composition still packed onbottom after 5 turns EX 7 17 33 6.3 Powdery redispersion EX 8 13 40 12Powdery redispersion EX 9 15 40 8 Powdery redispersion

Examples 10 to 17

Examples 10 to 13 describe some non-limiting examples of antiperspirantcompositions comprising a liquid activation enhancer, while Examples 14to 17 describe some non-limiting comparative examples of antiperspirantcompositions.

Ingredient EX 10 EX 11 EX 12 EX 13 EX 14 EX 15 EX 16 EX 17 Aluminum26.5%   26.5%   16.32%    26.37%    26.5%   26.5%   26.5%   26.5%  Chlorohydrate¹ Dimethicone² 38.18%    38.18%    32.14%    43%  38.18%   38.18%    38.18%    38.18%    Isopropyl Palmitate 9.05%   0% 0% 0% 0% 0%0% 0% Butyl Stearate 0% 9.05%   0% 0% 0% 0% 0% 0% Isopropyl Myristate 0%0% 29.98%    4% 0% 0% 0% 0% Mineral Oil 0% 0% 0% 0% 9.05%   0% 0% 0%Isohexadecane 0% 0% 0% 0% 0% 9.05%   0% 0% Octyldodecanol 0% 0% 0% 0% 0%0% 9.05%   0% PPG-14-Butyl 0% 0% 0% 0% 0% 0% 0% 9.05%   EtherHydrophilic tapioca 12.06%    12.06%    7.43%   12%  12.06%    12.06%   12.06%    12.06%    material³ Stearalkonium 4.27%   4.27%   4.25%  4.25%   4.27%   4.27%   4.27%   4.27%   Hectorite⁴ Triethyl Citrate1.39%   1.39%   1.38%   1.38%   1.39%   1.39%   1.39%   1.39%   SiliconeGum⁵ 0% 0% 0% 0.5%   0% 0% 0% 0% Liquid Fragrance 5.53%   5.53%   5.5%  5.5%   5.53%   5.53%   5.53%   5.53%   Material⁶ Complexed Beta 3.02%  3.02%   3% 3% 3.02%   3.02%   3.02%   3.02%   Cyclodextrin Total 100 100100 100 100 100 100 100 ¹86% assay of anhydrous active, average particlesize approximately 15 microns. ²DC 200 Fluid (50 centistoke) availablefrom Dow Corning ³Tapioca Pure from Akzo Nobel ⁴Bentone 38 availablefrom Elementis ⁵DC1503 (a mixture of dimethicone and dimethiconol)available from Dow Corning ⁶Is believed to have contained isopropylmyristate at less than 10% w/w of the liquid fragrance material

Examples 10 to 17 were prepared by mixing a first portion of thedimethicone; one of isopropyl myristate, isopropyl palmitate, butylstearate, mineral oil, isohexadecane, octyldodecanol and PPG-14-butylether; and disteardimonium hectorite by lightly stirring followed bymilling for at least 1 minute using a single head Silverson mill. Thetriethyl citrate was added next followed by at least five minutes ofmilling, followed by addition of the aluminum chlorohydrate, a secondportion of the dimethicone, the complexed BCDs, tapioca material,dimethicone/dimethiconol and liquid fragrance material. After making thecomposition, approximately 20 gms thereof was added to a clear glassaerosol bottle (Part # ATL-SC4-48 available from Aero-Tech LaboratoryEquipment Co of USA). The glass bottle was sealed with a valve assemblyand then approximately 40 gms of isobutane propellant was added to thebottle thru the valve assembly. Each sample was shaken to disperse thecomposition and hot tanked for four minutes at 130° F. After cooling,the samples were shaken again and allowed to stand for 24 hrs (long termsettling) prior to rotational and short term settling testing. Table 4below sets forth the long term settling height, short term settlingheight, average turns and observations related thereto for Examples 10to 17.

TABLE 4 Long Term Short Term Settling Settling Average Height HeightTurns (mm) (mm) (N = 3) Observations EX 10 14 38 8 Powdery redispersionEX 11 13 35 9 Powdery redispersion EX 12 10 25 7 Powdery redispersion EX13 15 38 6 Powdery redispersion EX 14 12 22 6 Composition falls off ofthe bottom in clumps and then redisperses EX 15 12 35 15 Compositionfalls off of the bottom in clumps and then redisperses. EX 16 11 24 9Composition falls off of the bottom in clumps and then redisperses.Composition was grainy - not homogenous EX 17 11 34 15 Composition fallsoff of the bottom in clumps and then redisperses. Composition wasgrainy - not homogenous

Examples 18 to 23

Examples 18 and 23 describe some non-limiting examples of antiperspirantcompositions comprising C12-15 alkyl benzoate and isopropyl myristate.

Ingredient EX 18 EX 19 EX 20 EX 21 EX 22 EX 23 EX 24 Aluminum 26.5%26.5% 26.5% 26.5% 26.5% 26.5% 26.37%    Chlorohydrate¹ 5 Centistoke45.22%  38.18%    0%   0%   0%   0% 0% Dimethicone² 10 Centistoke   0%  0% 38.18%    0%   0%   0% 0% Dimethicone² 20 Centistoke   0%   0%   0%38.18%  39.57%    0% 0% Dimethicone² 50 Centistoke   0%   0%   0%   0%  0% 38.18%  38%  Dimethicone² C12-15 Alkyl Benzoate 2.01% 9.05% 9.05%9.05% 9.05% 9.05% 0% Isopropyl Myristate   0%   0%   0%   0%   0%   0%9% Hydrophilic tapioca 12.06%  12.06%  12.06%  12.06%  12.06%  12.06% 12%  material³ Stearalkonium Hectorite⁴ 4.27% 4.27% 4.27% 4.27% 4.27%4.27% 4.25%   Triethyl Citrate 1.39% 1.39% 11.39%  1.39%   0% 1.39%1.38%   Silicone Gum⁵ —none none none none none none 0.5%   LiquidFragrance 5.53% 5.53% 5.53% 5.53% 5.53% 5.53% 5.5%   Material⁶ ComplexedBeta 3.02% 3.02% 3.02% 3.02% 3.02% 3.02% 3% Cyclodextrin Total 100 100100 100 100 100 100 ¹86% assay of anhydrous active, average particlesize approximately 15 microns. ²DC 200 Fluid (5, 10, 20 or 50centistoke) available from Dow Corning ³Tapioca Pure from Akzo Nobel⁴Bentone 38 available from Elementis ⁵DC1503 (a mixture of dimethiconeand dimethiconol) available from Dow Corning ⁶Is believed to havecontained isopropyl myristate at less than 10% w/w of the liquidfragrance material

Examples 18 to 23 were prepared by mixing a first portion of thedimethicone, C12-15 alkyl benzoate, and disteardimonium hectorite bylightly stirring followed by milling for at least 1 minute using asingle head Silverson mill. The triethyl citrate was added next followedby at least five minutes of milling, followed by addition of thealuminum chlorohydrate, a second portion of the dimethicone, thecomplexed BCDs, tapioca material, dimethicone/dimethiconol and liquidfragrance material. After making the composition, approximately 20 gmsthereof was added to a clear glass aerosol bottle (Part # ATL-SC4-48available from Aero-Tech Laboratory Equipment Co of USA). The glassbottle was sealed with a valve assembly and then approximately 40 gms ofisobutane propellant was added to the bottle thru the valve assembly.Each sample was shaken to disperse the composition and hot tanked forfour minutes at 130° F. After cooling, the samples were shaken again andallowed to stand for 24 hrs (long term settling) prior to rotational andshort term settling testing. Table 5 below sets forth the long termsettling height, short term settling height, average turns andobservations related thereto for Examples 18 to 23. Example 24 wasprepared according to the process shown in FIG. 14.

TABLE 5 Long Term Short Term Settling Settling Average Height HeightTurns (mm) (mm) (N = 3) Observations EX 18 12 25 15 Some clumping duringredispersion EX 19 15 40 7 Powdery redispersion EX 20 14 39 5 Powderyredispersion EX 21 13 35 9 Powdery redispersion EX 22 15 33 10 Powderyredispersion EX 23 9 10 15 Product falls off bottom in clumps and thenredisperses EX 24 12 31 6 Powdery redispersion

Examples 25 to 35 describe some non-limiting examples of combinations ofantiperspirant compositions and propellants. The concentration ofparticulates by weight of the total fill of materials (e.g.,antiperspirant composition plus propellant) is also set forth inExamples 25 to 35.

Ingredient EX 25 EX 26 EX 27 EX 28 EX 29 EX 30 EX 31 EX 32 EX 33 EX 34EX 35 Propellant (A-46) 50 50 50 0 0 0 0 0 0 0 0 Propellant (A-31) 0 0 050 0 50 50 65 65 65 65 Propellant (A-17) 0 0 0 0 50 0 0 0 0 0 0 Aluminum14 14 9.5 14 13.19 9.5 9.5 6.65 9.8 6.65 6.65 Chlorohydrate¹Dimethicone² 24.19 26.15 30.62 23.5 24.72 28 28 19.6 16.45 19.6 19.6Empty Beta 0 0 0 6 0 6 3 0 4.2 4.2 2.1 Cylcodextrin Hydrophilic 0 6 6 06 0 3 4.2 0 0 2.1 tapioca material³ Hydrophobic 6 0 0 0 0 0 0 0 0 0 0tapioca material⁴ Stearalkonium 1 0 0 1.5 2.13 1.5 1.5 1.05 1.05 1.051.05 Hectorite⁵ Triethyl Citrate 0.335 0 0 0.5 0.69 0.5 0.5 0.35 0.350.35 0.35 Hydrophilic 0 0.5 0.5 0 0 0 0 0 0 0 0 Silica Hydrophobic 00.125 0.125 0 0 0 0 0 0 0 0 Silica Silicone Gum⁶ 0.5 0 0 0.25 0.03 0.250.25 0.18 0.18 0.18 0.18 Lauryl Alcohol 0 0 0 1 0 1 1 0.7 0.7 0.7 0.7Fragrance 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.22 1.22 1.22 1.22Complexed Beta 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.05 1.05 1.05 1.05Cyclodextrin Total 100 100 100 100 100 100 100 100 100 100 100 % Total22.5 22.125 18 23 22.5 19 19 13 16 13 13 Particulates ¹86% assay ofanhydrous active, average particle size approximately 15 microns. ²DC200 Fluid (50 centistoke) available from Dow Corning ³Tapioca Pure fromAkzo Nobel ⁴Dry Flo TS from Akzo Nobel ⁵Bentone 38 available fromElementis ⁶DC1503 (a mixture of dimethicone and dimethiconol) availablefrom Dow Corning 7 Aerosil A300 silica from Evonik 8 Aerosil A300 silicafrom Evonik

The antiperspirant compositions of Examples 25 to 35 were made using thefollowing general batch method: the non-volatile silicone fluid wasadded to an appropriately sized container followed by the silica or clayand the mixture was milled for at least 1 minute at a speed of 10,000 to12,000 rpm using a hand held miller. If clay was added, triethyl citratewas also added to the mixture and milled for at least 5 minutes. Theantiperspirant active particles were added to the mixture and milled forat least 1 minute. The tapioca material, empty beta cylclodextrinmaterial and beta cyclodextrin fragrance materials as appropriate wereadded to the mixture and milled for at least one minute. The liquidfragrance material was then added along with a silicone gum, if desired,and milled for at least one minute.

The antiperspirant composition of Example 25 had an average viscosity ofapproximately 4,200 centipoise. The antiperspirant composition ofExample 26 had an average viscosity of approximately 3,000 centipoise,and the antiperspirant composition of Example 27 had an averageviscosity of approximately 1,500 centipoise. The viscosity measurementswere made using a Brookfield RVT Viscometer Model using an RV-4 spindleand techniques well known in the art.

Spray devices may be filled by transferring the desired weight(approximately 15 g) of the antiperspirant composition to a 55 mlcontainer and affixing a valve assembly. An appropriate amount of (A-46,A-31 or A-17) was propellant is added to the containers to achieve a 50%or 65% propellant concentration by weight of the total fill ofmaterials.

In Vivo Testing of Examples 25, 26, 27, Comparative Example 36 and aCommercial Product

Spray devices comprising the propellants and antiperspirant compositionsof Examples 25, 26, 27 and comparative Example 36 were prepared. Theantiperspirant composition of comparative Example 36 was made in amanner generally similar to that previously described for Examples 25 to27.

Ingredient EX 36 Propellant (A-46) 50 Aluminum Chlorohydrate 14Dimethicone 2.5 Cyclopentasiloxane 23.75 Hydrophilic Tapioca Material 6Hydrophilic Silica 0.5 Hydrophobic Silica 0.125 Fragrance 1.75 ComplexedBeta Cyclodextrin 1.5 Total 100 % Total Particulates 22.125

An in vivo study was conducted with spray devices comprising theantiperspirant compositions and propellant combinations of Examples 25,26, 27, comparative example 36 and a commercially available aerosolantiperspirant product. The packaging for the commercially availableaerosol antiperspirant product listed the following ingredients: butane,isobutene, propane, cyclomethicone, aluminum chlorohydrate, parfum,disteardimonium hectorite, dimethiconol, PVM/MA copolymer, sodium starchoctenylsuccinate, mannitol, alpha-isomethyl ionone, butylphenylmethylpropional, citronellol, eugenol, geraniol, hexyl cinnamal,1-limonene and linalool. The commercially available aerosolantiperspirant product had an average propellant concentration ofapproximately 85% (believed to be A-46 propellant) and an averagereservoir pressure of approximately 410 kPa. The commercially availableantiperspirant product also had an average total mass flow rate ofapproximately 1.02 g/sec, and an average antiperspirant composition massflow rate of approximately 0.20 g/sec.

Spray devices comprising the antiperspirant composition of Example 25had an average total mass flow rate of approximately 0.37 g/sec and anaverage antiperspirant composition flow rate of approximately 0.17g/sec. The spray devices comprising the antiperspirant composition ofExample 26 had an average total mass flow rate of approximately 0.38g/sec and an average antiperspirant composition flow rate ofapproximately 0.18 g/sec. The spray devices comprising theantiperspirant composition of Example 27 had an average total mass flowrate of approximately 0.36 g/sec and an average antiperspirantcomposition flow rate of approximately 0.17 g/sec. The spray devicescomprising the antiperspirant composition of comparative Example 36 hadan average total mass flow rate of approximately 0.39 g/sec and anaverage antiperspirant composition flow rate of approximately 0.18g/sec.

Forty-eight subjects were enrolled in the study, of which 45 completedthe study. The study lasted 26 days, comprising a 21 day washout periodin which the subjects used no antiperspirant products (deodorantproducts only were applied) followed by a 5 day treatment period withthe aerosol antiperspirant products. The antiperspirant products wereapplied once each morning during the 5 day treatment period. Hot roomevaluations for sweat production were conducted prior to start of the 5day treatment period (baseline) and 12 hours post the 5^(th) day of thetreatment period. The adjusted mean sweat values (mg sweat) at the startof the study (baseline) and twelve hours post treatment day 5 are shownbelow.

Mean Sweat at Baseline Adjusted Mean Baseline Sweat Value 12 hrs Post(mg of sweat Treatment Day #5 collected) (mg of sweat collected) SprayDevices with 595 382 Antiperspirant Composition of Example 25 SprayDevices with 591 362 Antiperspirant Composition of Example 26 SprayDevices with 665 343 Antiperspirant Composition of Example 27 SprayDevices with 676 405 Antiperspirant Composition of Comparative Example36 Commercially Available 591 439 Aerosol Antiperspirant Product

After five days of treatment, the spray devices comprising theantiperspirant compositions/propellants of Examples 25, 26 and 27resulted in lower mean sweat values (mg of sweat) twelve hours posttreatment day #5 than both the commercially available antiperspirantproduct and comparative Example 36. A lower mean sweat value means lessperspiration was released from the eccrine glands in the underarm area,resulting in a higher antiperspirant efficacy. The results for the spraydevices comprising the antiperspirant compositions of Examples 26 and 27were statistically significant (with at least a 90% confidence level).The results for the composition of Example 27 are particularly notable,as this composition had the lowest concentration of antiperspirantactive among Examples 25, 26 and 27 and yet had the lowest mean sweatvalue post treatment among the tested antiperspirant compositions. Thismay be due to the higher dimethicone concentration, which may haveincreased substantivity of the antiperspirant active on skin compared tothe antiperspirant compositions of Examples 25 and 26. The commerciallyavailable product, which had the highest propellant concentration, hadthe highest mean sweat value post treatment despite having the highestantiperspirant mass flow rate among the products. This may be due, atleast in part, to the low deposition efficiency of the commerciallyavailable product in combination with a lack of antiperspirant activesubstantivity resulting from the use of a volatile silicone fluid as theliquid carrier. The mean sweat value post treatment for theantiperspirant compositions of Example 26 were directionally better thanthe value for the compositions of Example 27, possibly due to thehydrophilic tapioca material enabling better antiperspirant activerelease compared to the hydrophobically modified tapioca material ofExample 27. The mean sweat value post treatment for antiperspirantcompositions of comparative Example 36 was directionally worse than thevalue for the antiperspirant composition of Example 26. This may be dueto reduced antiperspirant active substantivity resulting from use of thevolatile silicone fluid in the antiperspirant composition of comparativeExample 36 compared to use of a non-volatile silicone fluid in theantiperspirant compositions of Example 26.

Examples 37 to 48 describe some non-limiting examples of combinations ofantiperspirant compositions and propellants. The concentration ofparticulates by weight of the total fill of materials (e.g.,antiperspirant composition plus propellant) is also set forth inExamples 37 to 48.

EX 37 EX 38 EX 39 EX 40 EX 41 EX 42 Propellant A46 85.00 85.00 85.0085.00 85.00 85.00 Dimethicone 50 cst² 5.03 4.58 3.68 5.43 5.26 5.03Aluminum Chlorohydrate¹ 4.20 4.20 4.20 4.20 4.20 4.20 Tapioca Starch1.80 1.80 1.80 1.80 1.80 1.80 C12-C15 Alkyl Benzoate 1.02 1.02 1.02 1.021.02 1.02 Fragrance 1.05 1.05 1.05 1.05 1.05 1.05 PMX 1503 dimethiconeand 0.45 0.90 1.80 Dimethiconol⁶ Dimethicone 330M cps 0.05 0.22 0.45BCDs 0.45 0.45 0.45 0.45 0.45 0.45 Disteardimonium Hectorite 0.45 0.450.45 0.45 0.45 0.45 Isopropyl Myristate 0.41 0.41 0.41 0.41 0.41 0.41Triethyl Citrate 0.14 0.14 0.14 0.14 0.14 0.14 Total 100.00 100.00100.00 100.00 100.00 100.00 EX 43 EX 44 EX 45 EX 46 EX 47 EX 48Propellant A46 80.00 85.00 90.00 90.00 85.00 75.00 Dimethicone 50 cst²5.94 4.46 3.35 2.45 5.03 8.13 Aluminum Chlorohydrate¹ 6.67 5.00 2.802.80 4.20 7.25 Dry Flo Pure 1.40 1.05 1.20 1.20 1.80 3.00 C12-C15 AlkylBenzoate 1.22 0.92 0.68 0.68 1.02 1.70 Fragrance 1.60 1.20 0.70 0.701.05 1.75 PMX 1503 dimethicone and 0.60 0.45 0.30 1.20 0.45 0.75Dimethiconol⁶ BCDs 0.60 0.45 0.30 0.30 0.45 0.75 DisteardimoniumHectorite 0.80 0.60 0.30 0.30 0.45 0.75 Isopropyl Myristate 0.90 0.670.27 0.27 0.41 0.68 Triethyl Citrate 0.27 0.20 0.10 0.10 0.14 0.23 Total100.00 100.00 100.00 100.00 100.00 100.00

Examples 37 to 48 are made generally according to FIG. 13. The firststep comprises optionally mixing a first portion of the non-volatilesilicone fluid (e.g., 10% to 30% of the total concentration of the finalantiperspirant composition) with the clay material and the liquidactivation enhancer. The second step comprises adding a clay activatorto the mixture of the first step. This is followed by adding a secondportion of the non-volatile silicone fluid in a third step, after whichthe particulates are added in a fourth step to form a first composition.The first composition is filled into a reservoir of the spray device,after which the liquid fragrance material is added to the reservoir ofthe spray device to form the antiperspirant composition. The valveassembly is then attached to the spray device after which the propellantis added to the reservoir through the valve assembly. Significant mixingof the liquid fragrance material and the first composition is notbelieved to occur until the addition of the propellant, whichbeneficially dilutes both the liquid fragrance material and the firstcomposition thereby minimizing regions of high liquid fragrance materialconcentration that may negatively impact the desired bulking benefit ofthe clay material. Then the actuator is attached to the valve assembly.

FIG. 27 is a bar graph illustrating formulations with various siliconegum concentrations v. percent deposition of antiperspirant compositionin grams. The actual level of silicone gum (PMX 1503 dimethicone andDimethiconol and Dimethicone 330M cps) in finished product in examples37 to 42 are: EX 37 (0.054%); Ex 38 (0.108%); EX 39 (0.216%); EX 40(0.05%); EX 41 (0.22%) and EX 42 (0.45%). The deposition in grams are:EX 37 (0.22 grams); Ex 38 (0.25 grams); EX 39 (0.29 grams); EX 40 (0.21grams); EX 41 (0.23 grams) and EX 42 (0.25 grams). The bar graph in FIG.27 demonstrates the increase in the deposition in grams ofantiperspirant composition with increasing level of gum in finishedproduct, and also demonstrates that a higher molecular weight gum, PMX1503, is more efficient than a lower molecular weight gum, Dimethicone330M cps. The amount of deposition is measured according to the methodsin section “Antiperspirant Active Deposition Efficiency, AmountDispensed, and Amount Deposited”.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”. All numeric values (e.g., dimensions, flow rates,pressures, concentrations, etc.) recited herein may be modified by theterm “about”, even if not expressly so stated with the numeric value.

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A method of filling a hand held spray devicecomprising: providing a body having a reservoir comprising a total fillof materials; filling the reservoir with a first composition comprisinga non-volatile silicone fluid comprising an average viscosity from about3×10⁻⁶m²/s to about 350×10⁻⁶m²/s, an antiperspirant active, anorganoclay material, and at least one liquid that has a HansenSolubility Parameter for Hydrogen Bonding, δ_(h), between about 2 andabout 6 and a light transmittance value greater than 90% and wherein theat least one liquid comprises a combination of a first liquid selectedfrom the group consisting of ethyl stearate, propyl stearate, butylstearate, ethyl myristate, isopropyl myristate, ethyl palmitate,isopropyl palmitate, butyl palmitate, and combinations thereof and asecond liquid that is selected from the group consisting of stearylbenzoate, palmityl benzoate, C12-15 alkyl benzoate, and combinationsthereof; filling the reservoir with a second composition comprising aliquid fragrance material after the reservoir is filled with the firstcomposition; wherein the first composition and the second compositionform an antiperspirant composition comprising from about 2% to about 30%by weight of the antiperspirant composition, of the liquid, from about30% to about 50% by weight of the antiperspirant composition, ofnon-volatile silicone fluid; and from about 4% to about 10% by weight ofthe antiperspirant composition, of liquid fragrance material; providinga valve and attaching the valve to the body; and filling the reservoirwith a propellant wherein mixing of the first composition and the secondcomposition is provided by the introduction of the propellant into thereservoir; wherein the hand held spray device has a propellantconcentration after filling from about 30% to about 90% by weight of thetotal fill of materials within the reservoir; and wherein the firstcomposition further comprises a silicone gum having a concentration of0.3% to 1.2% by weight of the antiperspirant composition; and whereinthe viscosity of the antiperspirant composition is from about 2,000centipoise to about 50,000 centipoise.
 2. The method according to claim1, wherein the first liquid is selected from the group consisting ofisopropyl myristate, isopropyl palmitate, butyl stearate andcombinations thereof, and the second liquid is C12-15 alkyl benzoate. 3.The hand held spray device according to claim 1, wherein the organoclaymaterial is selected from the group consisting of stearalkoniumbentonite, disteardimonium hectorite, quaternium 90-bentonite, andcombinations thereof.
 4. The method according to claim 1, wherein thefirst composition further comprises a clay activator selected from thegroup consisting of propylene carbonate, triethyl citrate, methanol,ethanol, acetone, water and combinations thereof.
 5. The methodaccording to claim 3, wherein the organoclay material has aconcentration from about 1% to about 8% by weight of the antiperspirantcomposition.
 6. The method of claim 1, wherein the non-volatile siliconefluid comprises an average viscosity from about 50×10⁻⁶m²/s to about350×10⁻⁶m²/s.
 7. The method of claim 1, wherein the non-volatilesilicone fluid comprises an average viscosity from about 100×10⁻⁶m²/s toabout 350×10⁻⁶m²/s.
 8. The method according to claim 1, wherein thenon-volatile silicone fluid has a viscosity at the time of making fromabout 5×10⁻⁶m²/s to about 350×10⁻⁶m²/s.
 9. The method according to claim8, wherein the non-volatile silicone fluid had a viscosity at the timeof making from about 5×10⁻⁶m²/s to about 100×10⁻⁶m²/s.
 10. The methodaccording to claim 8, wherein the non-volatile silicone fluid comprisesa polydimethylsiloxane fluid having had an average molecular weight fromabout 500 to about 13,700 at the time of making.
 11. The methodaccording to claim 10, wherein the polymethylsiloxane fluid has theformula (II):M—D_(x—M) wherein M is (CH₃)₃SiO, D is ((CH₃)₂SiO) and X is from about 4to about
 183. 12. The method according to claim 1, wherein theantiperspirant composition is substantially free of a volatile siliconefluid.
 13. The method according to claim 1, wherein the second liquid isC12-15 alkyl benzoate and the non-volatile silicone fluid comprises apolymethylsiloxane fluid having had a viscosity less than 20 centistokesat the time of making.
 14. The method according to claim 1, wherein theantiperspirant composition is substantially free of mineral oil,isohexadecane, PPG-14 butyl ether and octyldodecanol.
 15. The method ofclaim 7, wherein the first liquid is isopropyl myristate.
 16. The methodaccording to claim 1, wherein the non-volatile silicone fluid comprisesa polymethylsiloxane fluid having a viscosity of about 50×10⁻⁶m²/s,wherein the first liquid is isopropyl myristate having a concentrationfrom about 2% to about 10% by weight of the antiperspirant compositionand wherein the liquid fragrance material has a concentration from about4% to about 6% by weight of the antiperspirant composition.
 17. Themethod according to claim 1, wherein the concentration of the liquidfragrance material by weight of the antiperspirant composition isgreater than the concentration of the organoclay material.
 18. Themethod according to claim 1, wherein the concentration of the liquidfragrance material by weight of the antiperspirant composition that isgreater than the concentration of the clay activator.
 19. The methodaccording to claim 1, wherein the antiperspirant composition has aviscosity from 1 Pa·s to about 50 Pa·s.